Herbicidal sulfonamides

ABSTRACT

Condensed ring aromatic ureas and isoureas are useful as plant growth regulants and as pre- and/or post-emergence herbicides.

RELATED APPLICATION

This application is a continuation-in-part of my copending applicationU.S. Ser. No. 098,724, filed Nov. 30, 1979, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to condensed ring aromatic ureas and isoureaswhich are useful as agricultural chemicals.

Netherlands Pat. No. 121,788, published on Sept. 15, 1966, discloses thepreparation of compounds of Formula 1 and their use as general orselective herbicides: ##STR1## wherein R₁ and R₂ may independently bealkyl of 1-4 carbon atoms; and

R₃ and R₄ may independently be hydrogen, chlorine or alkyl of 1-4 carbonatoms.

U.S. Pat. No. 4,127,405, issued to Levitt on Nov. 28, 1978, disclosescompounds of Formula 2, their agriculturally suitable salts, and methodsof using them as selective, as well as general, herbicides having bothpre-emergence and post-emergence activity: ##STR2## wherein R₁ can beselected from several aromatic possibilities including ##STR3## W isoxygen or sulfur; X is hydrogen, chlorine, bromine, methyl, ethyl,alkoxy of 1-3 carbon atoms, trifluoromethyl, CH₃ S-- or CH₃ OCH₂ ; and

Z is methyl or methoxy.

U.S. Pat. No. 4,120,691, issued to Levitt on Oct. 17, 1978, disclosescompounds of Formula 3, their agriculturally suitable salts, and methodsof using them as general herbicides having both pre-emergence andpost-emergence activity and as plant growth regulants: ##STR4## whereinR₁ can be selected from several aromatic possibilities including##STR5## W is oxygen or sulfur; and X and Z are independently hydrogen,methyl or methoxy.

U.S. Pat. No. 4,169,719, issued to Levitt on Oct. 2, 1979, disclosescompounds of Formula 4, their agriculturally suitable salts, and methodsof using them as selective, as well as general, herbicides having bothpre-emergence and post-emergence activity: ##STR6## wherein R₁ can beselected from several aromatic possibilities including ##STR7## W isoxygen or sulfur; X is hydrogen, chlorine, bromine, methyl, ethyl,alkoxy of 1-3 carbon atoms, trifluoromethyl, CH₃ S-- or CH₃ OCH₂ --; and

Z is methyl or methoxy.

The presence of undesired vegetation causes substantial damage to usefulcrops, especially agricultural products which satisfy man's basic foodand fiber needs, such as cotton, rice, corn, wheat, and the like. Thecurrent population explosion and concomitant world food and fibershortage demand improvements in the efficiency of producing these crops.Preventing or minimizing loss of a portion of such valuable crops bykilling, or inhibiting the growth of undesired vegetation is one way ofimproving this efficiency. Also, for man to conduct manufacturing,transportation, communications and other such activities, he must wage aconstant battle to prevent encroachment of undesirable vegetation intoareas where such activities are performed.

A wide variety of materials useful for killing or inhibiting(controlling) the growth of undesired vegetation is available; suchmaterials are commonly referred to as herbicides. A need still exists,however, for more effective herbicides.

SUMMARY OF THE INVENTION

According to this invention, there is provided compounds of Formulas 5and 6, which are useful as herbicides, and/or plant growth regulants.Some of the herbicides are useful for selective weed control in cropssuch as rice. ##STR8## wherein A¹ is H, F, Cl, Br, CH₃ O or NO₂ ;

A and A² are independently ##STR9## Cl, F, Br, NO₂, --CH₃, --SO₂ NR¹ R²,--SO₂ N(CH₃)(OCH₃), --S(O)_(n) R³, --OR³, --OSO₂ R³ or --OSO₂ CF₃ ;

B is ##STR10## n is 0, 1 or 2; Q is O, S or NR⁷ ;

R¹ is C₁ -C₄ alkyl;

R² is C₁ -C₄ alkyl;

R³ is C₁ -C₄ alkyl;

R⁴ is H or CH₃ ;

R⁵ is ##STR11## R⁶ is C₁ -C₆ alkyl; R⁷ is H, --OCH₃ or C₁ -C₄ alkyl;when Q is O or S then R⁸ is C₁ -C₆ alkyl; C₃ -C₆ alkenyl, CH₂ CH₂ OCH₃,CH₂ CH₂ OCH₂ CH₃, C₅ -C₆ cycloalkyl, C₄ -C₇ cycloalkylalkyl, phenyl,benzyl, or phenyl or benzyl substituted with one or two groups selectedfrom CH₃, Cl or OCH₃ ; and when Q is O, R⁸ may also be CH₂ CH₂ Cl; whenQ is R⁷ then R⁸ is H, C₁ -C₄ alkyl, C₃ -C₄ alkenyl and R⁸ and R⁷ takentogether can be --(CH₂)₄ --, --(CH₂)₅ -- or --CH₂ CH₂ OCH₂ CH₂ -- andwith the proviso that when R⁷ is CH₃ O, R⁸ is CH₃ ;

R⁹ is C₁ -C₆ alkyl, C₃ -C₆ alkenyl, C₅ -C₆ cycloalkyl, C₄ -C₇cycloalkylalkyl, benzyl, benzyl substituted with one or two groupsselected from CH₃, Cl or OCH₃ ;

R¹⁰ is H or CH₃ ;

R¹¹ is C₁ -C₃ alkyl;

R¹² is C₁ -C₄ alkyl or C₃ -C₆ alkenyl;

T is O or N-OR¹² ;

W is O or S;

X is CH₃, CH₃ O or CH₃ CH₂ O;

X² is O or CH₂ ;

Y is H, C₁ -C₃ alkyl, CH₃ OCH₂, CH₃ CH₂ OCH₂, OCH₂ CO₂ --(H or C₁ -C₂alkyl), OCH(CH₃)CO₂ (H or C₁ -C₂ alkyl), O--(C₁ -C₃ alkyl), O--(C₃ -C₄alkenyl) or NR¹⁰ R¹¹ ;

Y¹ is H, CH₃ or OCH₃ ;

Y² is H or CH₃ ; and

Z is N, CH or CCH₃ ;

and their agriculturally suitable salts.

Preferred for reasons of higher activity and/or lower cost and/orgreater ease of synthesis are:

(1) Compounds of formula 5 in which ##STR12## (2) Compounds of formula 6in which ##STR13##

More preferred in increasing order and for reasons of even higheractivity and/or lower cost and/or greater ease of synthesis are:

(3) Compounds of preferred 1 in which A is Cl, NO₂, CH₃, CH₃ O, CH₃ SO₂O, CH₃ SO₂, SO₂ N(CH₃)₂, SO₂ N(CH₃)(OCH₃), CH₃ S or CH₃ SO;

(4) Compounds of preferred 3 in which A¹ is H;

(5) Compounds of preferred 4 in which Y is CH₃ or CH₃ O; X² is O, and Y²is CH₃ ;

(6) Compounds of preferred 5 in which A is Cl;

(7) Compounds of preferred 2 in which A² is Cl, NO₂, CH₃, CH₃ O, CH₃ SO₂O, CH₃ SO₂, SO₂ N(CH₃)₂, SO₂ N(CH₃)(OCH₃), CH₃ S or CH₃ SO;

(8) Compounds of preferred 7 in which A¹ is H;

(9) Compounds of preferred 8 in which X² is O, Y is CH₃ or CH₃ O and Y²is CH₃ ;

(10) Compounds of preferred 9 in which A² is Cl.

It is noted that compounds of preferred 10 demonstrate selective weedcontrol in rice.

Specifically preferred for reasons of highest activity and/or lowestcost and/or greatest ease of synthesis are:

2-chloro-N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide;

2-chloro-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide;

2-chloro-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide;

2-chloro-N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide;

2-chloro-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide;

2-chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide;

2-chloro-N-[(5,6-dihydro-4-methylfuro[2,3-d]pyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide;

2-chloro-N-[(5,6-dihydro-4-methoxyfuro[2,3-d]pyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide;

2-chloro-N-[(4,6-dimethylfuro[2,3-d]pyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide;

8-chloro-N-[(4,6-dimethylpyrimidine-2-yl)aminocarbonyl]-1-naphthalenesulfonamide;

8-chloro-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide;

8-chloro-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide;

8-chloro-N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide;

8-chloro-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide;

8-chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide;

8-chloro-N-[(5,6-dihydro-4-methylfuro[2,3-d]pyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide;

8-chloro-N-[(5,6-dihydro-4-methoxyfuro[2,3-d]pyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide;and

8-chloro-N-[(4,6-dimethylfuro[2,3-d]pyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide.

The following novel compounds of Formulas 7, 8, 43 and 44 are useful asintermediates:

    ______________________________________                                         ##STR14##              where Z is CH or N and A and A.sup.1 are as                                   previously defined;                                    ##STR15##              where Z is CH or N and A.sup.1 and A.sup.2 are as                             reviously defined;                                     ##STR16##              where A and A.sup.1 are as previously defined and                             A is not CH.sub.3 SO;                                  ##STR17##              where A.sup.1 and A.sup.2 are as previously                                   defined and A.sup.2 is not CH.sub.3 SO.               ______________________________________                                    

Specifically preferred intermediates are: 8-chloronaphthalenesulfonylisocyanate; and 2-chloronaphthalenesulfonyl isocyanate.

SYNTHESIS

Many of the compounds of 5 and 6 are prepared as shown in Equation 1 bythe reaction of an appropriately substituted naphthalenesulfonylisocyanate or isothiocyanate with an appropriate aminopyrimidineor aminotriazine. ##STR18##

The addition of the sulfonylisocyanate and the heterocyclic amine can beeffected in methylene chloride, dry acetonitrile or dry tetrahydrofuranby heating under reflux protected from moisture. The products can beisolated by evaporation of the solvent under reduced pressure andcautious elutriation of the residue. Chromatography (silica gel orflorisil) may also be required.

The preparation of the substituted sulfonylisocyanates 7 and 8 can bebroadly envisioned from the corresponding sulfonamide. ##STR19##

The reaction of 9 or 10 as in (3) or (4) may be effected by heating withan alkyl isocyanate, e.g., butyl isocyanate and a catalytic amount of1,4-diazobicyclo[2,2,2]octane (DABCO) in xylene or some other inertsolvent of sufficiently high boiling point, e.g., >135°, toapproximately 130°-160° C. Phosgene is added to the mixture until anexcess of phosgene is present as indicated by depression of the boilingpoint.

After the mixture is cooled, the product solution may be separated bydecantation or filtration to remove small amounts of insolubleby-product, and the solvent and alkyl isocyanate may be distilled underreduced pressure. The crude sulfonylisocyanate may be used withoutfurther purification.

When 9 or 10 contains a base labile A² or A, the preparation of thesulfonamide and its subsequent phosgenation as described by H. Ulrich,B. Tucker and A. A. R. Sayigh, J. Org. Chem., 34, 3200 (1969), may beused to prepare 7 or 8 respectively.

The required sulfonamides 9 or 10 may be prepared by several procedures.Most generally, the sulfonamides may be prepared from the sulfonylchlorides 11 and 12 as described in "Preparative Organic Chemistry", ed.G. Hilgetag and A. Martini, J. Wiley and Sons, New York (1972). Thesulfonyl chlorides may be prepared by chlorination of the sulfonic acids13 and 14, by methods described by Hilgetag and Martini, op. cit. Thepreparation of these acids is described in the art. These compounds maybe further transferred by methods known in the art to yield otherdisclosed sulfonic acids. ##STR20##

Sulfonyl chlorides may also be prepared from an appropriatelysubstituted naphthoic acid 15. The oxazoline 16 may be prepared andmetalated as described by A. I. Meyers, D. L. Temple, D. Haldukewych andE. D. Mihelich, J. Or. Chem., 39, 2787 (1974) and E. D. Mihelich and A.I. Meyers, J. Org. Chem., 40 3158 (1975). Trapping of anion with adisulfide can be effected following the procedure of H. W. Gschwend andA. Hamdan, J. Org. Chem., 40, 2008 (1975) to yield 17. ##STR21##Oxidation of this ether to the sulfonyl chloride with concommitantdeprotection of the acid may be effected after R. F. Langler, Z. A.Marini and E. S. Spalding, Can. J. Chem., 57, 3193 (1979).

Appropriately functionalyzed naphthalene sulfonimides 18 may also serveas precursors to 9. The required intermediates may be prepared accordingto H. P. Haufmann and H. Zobel, Ber., (1922) 1499, as shown in Equation(10). ##STR22##

Opening of the naphthalene sulfonimide by acid catalyzed alcoholysis maybe effected, to yield 9. A² may be further transformed as will bedescribed later to other functional groups used in this invention.

Naphthalene sulfonimides 18 may also be prepared by oxidation of thecorresponding naphthalene isothiazole 19 after the work of G. Steiner,J. Liebigs Ann., (1978) [4] 635. The naphthalene isothiazoles may beprepared from a suitably functionalized 2-naphthaldehyde by the methodof H. Hagen and H. Flieg, Fed. Rep. Germany Pat. No. 2503699 (May 8,1976). ##STR23##

Naphthalene sulfonamide 10 may be prepared after the work of J. G.Lombardino, J. Org. Chem., 36 1843, (1971), where A can be anelectrophilic group and A¹ is not an electrofuge in the 7-position. Asubstituted naphthalene sulfonyl chloride is allowed to react with anamine. The resulting sulfonamide 20 may be metalated and trapped with anelectrophile. The amide protecting group can be removed by methods knownin the art. ##STR24##

Where X=sulfur in 5 and 6, the useful sulfonyl isothiocyanateintermediates 22 and 24 may be prepared by reaction of the sulfonamide 9or 10 with carbon disulfide when A or A² is not base labile as shown in(13) and (14). ##STR25##

The substituted sulfonamide is dissolved in dimethylformamide (DMF) withan equivalent amount of carbon disulfide. Two equivalents of potassiumhydroxide are added portionwise at room temperature. The resultingmixture is stirred for 1-8 hours and diluted with ethyl acetate, diethylether or a similar aprotic solvent to cause the dipotassium salt of thedithiocarbamic acid to precipitate. The salt may be isolated, dried andsuspended in an inert solvent such as xylene, benzene, carbontetrachloride or methylene chloride. Phosgene is added to the stirredsuspension at a temperature of about -20° to 25° C. and the mixturestirred for 1-3 hours.

The sulfonylisothiocyanate which is formed is usually soluble in thesolvent and is isolated by filtering off the inorganic potassiumchloride and concentrating the filtrate. These isothiocyanates may beunstable and tend to dimerize readily, however, the dimers can be usedin the same manner as the parent isothiocyanates for the purpose of theinvention.

As shown in (15) and (16), when W=sulfur, 5 and 6 may be prepared byreacting 22 or 24 with a substituted heterocyclic amine.

    22+HNR.sub.4 R.sub.5 →6                             (15)

    24+HNR.sub.4 R.sub.5 →5                             (16)

The reactions of (15) and (16) may be carried out in the mannerdescribed for (1) and (2).

Many compounds of 6 or 5 where W=sulfur may also be prepared by thereaction of appropriately substituted 9 or 10 with a heterocyclicisothiocyanate, SCNR₅.

    9+SCNR.sub.5 →6                                     (17)

    10+SCNR.sub.5 →5                                    (18)

These reactions may best be carried out by dissolving or suspending thesulfonamide and isothiocyanate in a polar solvent such as acetone,acetonitrile, ethyl acetate or methylethyl ketone, adding an equivalentof a base such as potassium carbonate, and stirring the mixture at atemperature from ambient up to reflux for one to twenty four hours. Insome cases, the product precipitates from the reaction mixture and canbe removed by filtration. The product is stirred in dilute mineral acid,filtered, and washed with cold water. If the product does notprecipitate from the reaction mixture, it can be isolated by evaporationof the solvent, elutriation of the residue with dilute mineral acid, andfiltering to obtain the insoluble product.

The heterocyclic isothiocyanates which are used may be prepared forexample, according to the method of Japan Patent ApplicationPublication: Kokai No. 51-143686, June 5, 1976, or that of W. Abrahamand A. Barnikow, Tetrahedron 29, 691-7 (1973).

When ##STR26## and W=oxygen, 6 and 5 may be prepared as shown in (19)and (20). ##STR27##

An equivalent or excess amount of carbon tetrachloride is added to asolution of 5 or 6 and triphenyl phosphine in an inert aprotic solventsuch as acetronitrile at about -10° to 25° C. The resulting reaction iscompleted by stirring at the designated temperature for 10 to 48 hoursto obtain a carbamimidoyl halide 25 or 27,which may be isolated bypassing the reaction solution through a silica gel column to remove thetriphenyl phosphine oxide and then removing the solvent by evaporationunder reduced pressure.

25 or 27 may be converted directly to 26 or 28 by reacting the reactionmixture with a metal alkoxide at -10° to 25° C. The reaction iscompleted by stirring at ambient temperature for 2 to 24 hours. Thecrude products 28 or 26 are isolated by filtering off precipitated metalhalide and removing the solvent by evaporation under reduced pressure.Further purification may be accomplished by recrystallization or columnchromatography on silica gel.

When W=oxygen and ##STR28## and A or A² is not a base labile functionalgroup, particularly when R⁵ is pyrimidinyl; 26 and 28 may be prepared asdescribed in (21) and (22). ##STR29##

29 and 31 are known in the art, R. Gompper and W. Hagele, Chem. Ber.,99, 7885 (1966). 30 and 32 may be prepared by allowing 29 and 31 toreact with sulfuryl chloride in an inert organic solvent such asmethylene chloride or chloroform at a temperature between -10° to 30° C.30 and 32 may be isolated by evaporation of the solvent.

The lithium salt of the corresponding 2 -aminoheterocyclic compound canbe prepared by reacting the aminoheterocyclic compound with n-butyllithium in a solvent such as tetrahydrofuran. To this salt solution isadded a solution of 30 or 32 in tetrahydofuran at a temperature of about-10° to 10° C. The reaction mixture is then stirred at 0°-10° C. forabout 1-2 hours and at ambient temperature for about 1-4 hours. Theproducts of 26 and 28 are isolated by filtering off the inorganic saltsand removing the solvent under reduced pressure. The product may befurther purified by recrystallization or by column chromatography onsilica gel.

When W=sulfur and ##STR30## and A or A² is not base labile, 6 and 5 maybe prepared by reacting the salt 33 or 34 with an alkylating agent R⁶ Dwhere D is a sulfate, chloride, bromide, or iodide and M is alkalimetal, as shown in (23) and (24). ##STR31##

A solution of 5 or 6, W=sulfur is allowed to react with a strong basesuch as methyl lithium in dry tetrahydrofuran or other suitable solventprotected from moisture at -20°-60° C. The resulting anionic species maybe trapped with the addition of a alkylating reagent R⁶ D. The productis isolated by evaporation of the solvent and recrystallization of theresulting residue from a solvent such as acetonitrile or ethyl alcohol.

When Q is NR⁷, 36 may be prepared from those compounds where ##STR32##Q=oxygen and R=methyl by reaction with dialkyl aluminum-N-alkylamidederivatives as shown in (25). ##STR33##

The intermediate alkylaminoaluminum compounds, prepared according to theteaching of A. Busha, M. Lipton and S. W. Weinreb, Tetrahedron Letters4171 (1977), are co-mingled with a suspension of the esters in toluene,or similar inert solvent and the mixture is refluxed for one to sixhours. The product may be isolated by evaporating the solvent, addingmethylene chloride and aqueous hydrochloric acid to decompose theresidual reaction mass and extracting the desired product into methylenechloride. Evaporation of the separated methylene chloride yields thedesired product which can be purified by recrystallization from an inertsolvent or by chromatography on silica gel.

When Q=sulfur, 37 may be prepared via the analogous reaction of 35 withthe appropriate dialkylaluminum alkylthiolate as shown in (26) ##STR34##

The aluminum thiolate used in these reactions can be prepared accordingto the method of R. P. Hatch and S. W. Weinreb, Journal of OrganicChemistry, 42, 3960 (1977). The reaction of the thiolate is best carriedout in a neutral solvent such as toluene or xylene at reflux for one tothree hours. Best results may be obtained when the aluminum thiolatecompound is present in excess of the stoichiometric amount required. Thecompounds may be isolated as described for 36.

When ##STR35## and W=oxygen, and A¹ =H or CH₃ O, 39 may be prepared bythe directed ortho lithiation of 6 where A² =Cl or Br and trapping ofthe anionic species with an acylating agent as shown in (27). (27)##STR36##

A solution of 38 in tetrahydrofuran or any suitable ethereal solvent maybe allowed to react with excess alkyl lithium at temperatures of -40° to50° C. The resulting polyanionic species may be captured by theacylating agent. Quenching of the product with saturated ammoniumchloride may yield only the desired 39 as a stable reaction product.

The synthesis of a wide variety of organolithium compounds by manydifferent procedures is known in the art. A summary of methods withbibliography is contained in Organo-Metallic Compounds, G. E. Coates,John Wiley and Sons, 1960, p. 3-21.

When T=N--OR³, 6 may be prepared by standard oximation methods asoutlined in Preparative Organic Chemistry, G. Hilgetag and A. Martini,Ed., John Wiley and Sons, p. 513.

The synthesis of heterocyclic amines has been reviewed in "The Chemistryof Heterocyclic Compounds", published by Interscience Publ., New Yorkand London. 2-aminopyrimidines are described by D. J. Brown in Vol. XVIof this series. The 2-amino-1,3-5-triazine are reviewed by K. R. Huffmanand in "The Triazines" of this same series. The synthesis of triazinesis also described by F. C. Schaefer, U.S. Pat. No. 3,154,547 and by K.R. Huffmann and F. C. Schaeffer, J. Org. Chem. 28, 1816 (1963).

Braker, Sheehan, Spitzmiller and Lott, J. Am. Chem. Soc. 69, 3072 (1947)describe the preparation of6,7-dihydro-4-methoxy-5H-cyclopentapyrimidin-2-amine by the followingsequence of reactions. ##STR37##

An analogous sequence of reactions can be used to prepare5,6,7,8-tetrahydro-4-methoxy-2-quinazolinamine. ##STR38##

Mitter and Bhattacharya, Quart. J. Indian Chem. Soc. 4, 152 (1927)describe the preparation of5,6,7,8-tetrahydro-4-methyl-2-quinazolinamine as follows: ##STR39##

An analogous sequence of reactions can be used to prepare6,7-dihydro-4-methyl-5H-pyrano[2,3-d]pyrimidin-2-amine starting with2-acetyl-8 valerolactone [Korte and Wusten, Tetrahedron 19, 1423(1963)]. ##STR40##

6,7-Dihydro-4-hydroxy-5H-pyrano[2,3-d]pyrimidin-2-amine can be preparedfrom diethyl 3-chloropropylmalonate, guanidine carbonate and sodiumethoxide in ethanol. Treatment of the product ##STR41## with phosphorusoxychloride gives 4-chloro-6,7-dihydro-5H-pyrano[2,3-d]pyrimidin-2-amineand subsequent reaction with sodium methoxide in refluxing methanolaffords 6,7-dihydro-4-methoxy-5H-pyrano[2,3-d]pyrimidin-2-amine.

Compounds of R⁵ where Y¹ is ethoxy can be prepared by a procedureanalogous to the methoxy derivatives.

The furo[2,3-d]pyrimidine intermediates 42 where Y² is CH₃ have beenreported in the literature of E. Bisagni et al., Bull. Soc. Chim. Fr.,(1969) 803. An apparently more efficient procedure is depicted in (28).##STR42##

The keto-ester precursors 40 are prepared by well-known literaturemethods, e.g, J. F. Tinker and T. E. Whatmough, J. Amer. Chem. Soc. 745235 (1952).

Treatment of 40 with an excess of guanidine carbonate in a polar aproticsolvent such as dimethylsulfoxide (DMSO), at elevated temperatures,ambient pressure and preferably under an inert atmosphere, yields both42 and 41 as products; the products are isolated upon dilution of thereaction mixture with acetone and water successively. The relativeamounts of 42 and 41 isolated may be adjusted by varying the reactiontime and/or temperature. Higher reaction temperatures and longerreaction times (e.g., 140° for 6 hours) favor the production of thefuropyrimidine 42 over the uncyclized pyrimidine 41.

Agriculturally suitable salts of compounds of formulae 5 and 6 will alsobe useful herbicides and can be prepared by methods well-known in theart.

Starting materials and intermediates used to prepare compounds of thisinvention but not otherwise described herein, are disclosed in U.S. Pat.No. 4,127,405 and prior patent application U.S. Ser. No. 910,965, nowabandoned.

The invention is further illustrated by the following examples in whichall temperatures are in degrees centigrade and all percentages are byweight unless otherwise specified.

EXAMPLE 1 Methyl1-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-aminosulfonyl-2-naphthalenecarboxylate

A mixture containing 1.6 g of 2-amino-4,6-dimethoxypyrimidine, 30 ml ofanhydrous methylene chloride and of2-carbomethoxynaphthalenesulfonylisocyanate can be stirred at ambienttemperature and pressure for 16 hours. It can then be filtered to removeunreacted amine and the filtrate evaporated at a temperature up to 40°and at reduced pressure. The resulting residue may be elutriated withchlorobutane or a chlorobutane-methylene chloride and the solid productnamed above separated by filtration and dried.

EXAMPLE 22-chloro-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide

To 3 ml of a methylene chloride solution of 0.59 g (0.0042 mol) of2-amino-4,6-dimethoxypyrimidine in a magnetically stirred 50 ml roundbottom flask protected from moisture was added 2 ml of a methylenechloride solution containing 1 g (0.004 mol) of2-chloro-1-naphthalenesulfonylisocyanate. The reaction mixture wasallowed to stir at room temperature for 18 hours. The solvent wasremoved in vacuo to yield the crude product. The product was purified byelutriation with chlorobutane as previously described to yield a paleyellow solid, m.p. 165°-168°.

The following compounds were similarly prepared:

2-chloro-N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide,m.p. 210°;

2-chloro-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide,m.p. 115°;

2-chloro-N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide,m.p. 95°-100°;

2-chloro-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide,m.p. 125°; and

2-chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide,m.p. 78°-80°.

EXAMPLE 3 Methyl 1-[[(4,6-dimethoxypyrimidin-2-ylamino)(methylthio)methylene]aminosulfonyl]-2-naphthalenecarboxylate

To a suspension of methyl1-[[(4,6-dimethoxypyrimidin-2-yl)aminothiocarbonyl]aminosulfonyl]-2-naphthalenecarboxylatein 200 ml of anhydrous tetrahydrofuran can be added 16.7 ml of 3 MNaOCH₃ /MeOH solution. The resulting reaction mixture can be heated toreflux, 3.1 ml of methyl iodide in 10 ml of anhydrous tetrahydrofurancan be added; and the reaction mixture can be refluxed for 3 hours. Thereaction mixture can be cooled to cause the formation of a precipitatewhich can be filtered off and washed with tetrahydrofuran to afford thedesired product.

EXAMPLE 4N,N-dimethyl-1-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]-2-naphthalenecarboxamide

To 0.01 mole of the compound of Example 1 in 75 ml of toluene can beadded 37 ml of a methylene chloride and toluene solution (3:5)containing 1.25 g of dimethylaluminum dimethylamide with stirring atambient temperature. The resulting mixture can be heated to reflux for 2hours, cooled, then 10 ml of methanol can be added and the solventsevaporated in vacuo. The resulting residue can be treated with a mixtureof methanol, water, and dilute hydrochloric acid and the precipitatedproduct filtered off to yield the desired product. Extraction of theaqueous filtrate with methylene chloride will give more product.

EXAMPLE 58-nitro-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide

To 0.55 g (0.004 mol) of 2-amino-4-methoxy-6-methylpyrimidine dissolvedin 5 ml of dry methylene chloride in a magnetically stirred 50 ml roundbottom flask equipped with reflux condenser protected from moisture wasadded 4 ml of a methylene chloride solution of 1.0 g (0.004 mol) of8-nitro-1-naphthalenesulfonylisocyanate. The reaction mixture wasstirred with heating under reflux for ˜16 hours. The cooled reactionmixture was concentrated in vacuo. The crude product was isolated byelutriation with chlorobutane in the usual manner to yield an off whitesolid, m.p. 145°-154°.

The following compounds were similarly prepared:

8-nitro-N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide,m.p. 178°-183°;

8-nitro-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide,m.p. 158°-160°;

8-nitro-N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide,m.p. 95°-100°;

8-nitro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-aminocarbonyl]-1-naphthalenesulfonamide,m.p. 152°-158°; and

8-nitro-N-[(4,6-dimethoxy-1,3,-5-triazin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide,m.p. 164°-170°.

Following the methods of the above examples and the general proceduresdescribed, the compounds in the following tables can be prepared byusing the appropriate heterocyclic and aromatic moiety. These tablesalso illustrate the scope of this invention.

                                      TABLE I                                     __________________________________________________________________________     ##STR43##                                                                    A.sup.2          A.sup.1                                                                            R.sup.4                                                                          W X     Y           Z                                __________________________________________________________________________    Cl               H    H  O CH.sub.3                                                                            CH.sub.3    CH                               Cl               H    H  O CH.sub.3 O                                                                          CH.sub.3    CH                               Cl               H    H  O CH.sub.3 O                                                                          CH.sub.3 O  CH                               Cl               H    H  O CH.sub.3                                                                            CH.sub.3    N                                Cl               H    H  O CH.sub.3                                                                            CH.sub.3 O  N                                Cl               H    H  O CH.sub.3 O                                                                          CH.sub.3 O  N                                Br               H    H  O CH.sub.3                                                                            OCH.sub.3   CH                               Br               H    H  O CH.sub.3 O                                                                          CH.sub.3    N                                Br               H    H  O CH.sub.3 O                                                                          CH.sub.3 O  CH                               Br               H    H  S CH.sub.3                                                                            CH.sub.3 O  CCH.sub.3                        F                H    H  O CH.sub.3 CH.sub.2 O                                                                 H           CH                               F                H    H  O CH.sub.3 O                                                                          CH.sub.3    CH                               F                H    H  O CH.sub.3                                                                            CH.sub.3 O  N                                F                H    H  O CH.sub.3 O                                                                          CH.sub.3 O  CH                               NO.sub.2         H    H  O CH.sub.3 O                                                                          CH.sub.3    CH                               NO.sub.2         H    H  O CH.sub.3                                                                            CH.sub.3 O  N                                NO.sub.2         H    H  O CH.sub.3 O                                                                          CH.sub.3 O  CH                               NO.sub.2         4-Cl H  O CH.sub.3 O                                                                          CH.sub.3 OCH.sub.2                                                                        CH                               CH.sub.3         8-NO.sub.2                                                                         CH.sub.3                                                                         O CH.sub.3                                                                            CH.sub.3 CH.sub.2 OCH.sub.2                                                               N                                SO.sub.2 N(CH.sub.3)(CH.sub.3 CH.sub.2)                                                        H    H  O CH.sub.3                                                                            CH.sub.3 O  CH                               SO.sub.2 N(CH.sub.3 CH.sub.2).sub.2                                                            H    H  O CH.sub.3 O                                                                          CH.sub.3 O  CH                               SO.sub.2 N(CH.sub.3)[CH(CH.sub.3).sub.2 ]                                                      H    H  O CH.sub.3                                                                            CH.sub.3 O  N                                SO.sub.2 N(CH.sub.3)(CH.sub.3 CH.sub.2 CH.sub.2)                                               H    H  O CH.sub.3 O                                                                          CH.sub.3 CH.sub.2 CH.sub.2                                                                CCH.sub.3                        SO.sub.2 N[CH.sub.2 CH(CH.sub.3).sub.2 ] [CH(CH.sub.3).sub.2 ]                                 5-OH H  S CH.sub.3                                                                            OCH.sub.2 CO.sub.2 CH.sub.3                                                               N                                SO.sub.2 N(CH.sub.3)(OCH.sub.3)                                                                6-Br CH.sub.3                                                                         O CH.sub.3 O                                                                          OCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3                                                      CH                               SO.sub.2 N(CH.sub.3)(OCH.sub.3)                                                                H    H  O CH.sub.3                                                                            CH.sub.3 O  CH                               SO.sub.2 N(CH.sub.3)(OCH.sub.3)                                                                H    H  O CH.sub.3 O                                                                          CH.sub.3 O  CH                               OSO.sub.2 (CH.sub.2 CH.sub.2 CH.sub.3)                                                         H    H  O CH.sub.3                                                                            CH.sub.3 O  CH                               OSO.sub.2 (CH.sub.2 CH.sub.3)                                                                  H    H  O CH.sub.3 O                                                                          CH.sub.3 O  CH                               OSO.sub.2 (CH.sub.2 CH(CH.sub.3).sub.2)                                                        3-Cl H  S CH.sub.3 O                                                                           ##STR44##  N                                OSO.sub.2 (CH.sub.3)                                                                           7-F  H  O CH.sub.3                                                                             ##STR45##  CH                               O(CH.sub.2 CH.sub.2 CH.sub.3)                                                                  5-OCH.sub.3                                                                        H  O CH.sub.3 O                                                                          OCH(CH.sub.3).sub.2                                                                       CH                               O(CH.sub.3)      H    CH.sub.3                                                                         O CH.sub.3                                                                            OCH.sub.2 CH.sub.3                                                                        N                                O(CH.sub.2 CH.sub.3)                                                                           H    H  O CH.sub.3 O                                                                          CH.sub.3 O  CH                               O(CH(CH.sub.3)CH.sub.2 CH.sub.3)                                                               H    H  O CH.sub.3                                                                            CH.sub.3 O  CH                               S(CH(CH.sub.3).sub.2)                                                                          H    H  O CH.sub.3                                                                            CH.sub.3 O  CH                               S(CH.sub.2 CH(CH.sub.3).sub.2)                                                                 H    H  O CH.sub.3 O                                                                          CH.sub.3 O  CH                               S(CH.sub.2 CH.sub.3)                                                                           4-Br H  S CH.sub.3 O                                                                          OCH.sub.2 CHCH.sub.2                                                                      CH                               SO.sub.2 (CH.sub.3)                                                                            H    H  O CH.sub.3 O                                                                          CH.sub.3    CH                               SO.sub.2 (CH.sub.3)                                                                            H    H  O CH.sub.3 O                                                                          CH.sub.3 O  CH                               SO.sub.2 (CH.sub.3)                                                                            H    H  O CH.sub.3                                                                            CH.sub.3    CH                               SO.sub.2 (CH.sub.3)                                                                            H    H  O CH.sub.3                                                                            CH.sub.3    N                                SO.sub.2 (CH.sub.3)                                                                            H    H  O CH.sub.3                                                                            CH.sub.3 O  N                                SO.sub.2 (CH.sub.3)                                                                            H    H  O CH.sub.3 O                                                                          CH.sub.3 O  N                                OSO.sub.2 CF.sub.3                                                                             8-Cl H  O CH.sub.3                                                                             ##STR46##  N                                __________________________________________________________________________

                  TABLE II                                                        ______________________________________                                         ##STR47##                                                                    A.sup.2    A.sup.1                                                                             R.sup.4 W    R.sup.5                                         ______________________________________                                        Cl         H     H       O                                                                                   ##STR48##                                      Cl         H     H       O                                                                                   ##STR49##                                      Cl         H     H       O                                                                                   ##STR50##                                      Cl         H     H       O                                                                                   ##STR51##                                      Cl         H     H       O                                                                                   ##STR52##                                      Cl         H     H       O                                                                                   ##STR53##                                      Cl         H     H       O                                                                                   ##STR54##                                      Cl         H     H       O                                                                                   ##STR55##                                      SO.sub.2 (CH.sub.3)                                                                      H     H       O                                                                                   ##STR56##                                      SO.sub.2 (CH.sub.3)                                                                      H     H       O                                                                                   ##STR57##                                      SO.sub.2 (CH.sub.3)                                                                      H     H       O                                                                                   ##STR58##                                      SO.sub.2 (CH.sub.3)                                                                      H     H       O                                                                                   ##STR59##                                      SO.sub.2 (CH.sub.3)                                                                      H     H       O                                                                                   ##STR60##                                      SO.sub.2 (CH.sub.3)                                                                      H     H       O                                                                                   ##STR61##                                      SO.sub.2 (CH.sub.3)                                                                      H     H       O                                                                                   ##STR62##                                      SO.sub.2 (CH.sub.3)                                                                      H     H       O                                                                                   ##STR63##                                      ______________________________________                                    

                                      TABLE III                                   __________________________________________________________________________     ##STR64##                                                                    A                 A.sup.1                                                                            R.sup.4                                                                          W X     Y            Z   m.p.                       __________________________________________________________________________                                                       (°C.)               Cl                H    H  O CH.sub.3                                                                            CH.sub.3     CH                             Cl                H    H  O CH.sub.3 O                                                                          CH.sub.3     CH  158-161°            Cl                H    H  O CH.sub.3 O                                                                          CH.sub.3 O   CH                             Cl                H    H  O CH.sub.3                                                                            CH.sub.3     N                              Cl                H    H  O CH.sub.3 O                                                                          CH.sub.3     N   98°                 Cl                H    H  O CH.sub.3 O                                                                          CH.sub.3 O   N                              NO.sub.2          H    H  O CH.sub.3                                                                            CH.sub.3     CH                             NO.sub.2          H    H  O CH.sub.3                                                                            CH.sub.3 O   CH                             NO.sub.2          H    H  O CH.sub.3 O                                                                          CH.sub.3 O   CH                             NO.sub.2          H    H  O CH.sub.3                                                                            CH.sub.3     N                              NO.sub.2          H    H  O CH.sub.3                                                                            CH.sub.3 O   N                              NO.sub.2          H    H  O CH.sub.3 O                                                                          CH.sub.3 O   N                              SO.sub.2 (CH.sub.3)                                                                             H    H  O CH.sub.3                                                                            CH.sub.3     N                              SO.sub.2 (CH.sub.3)                                                                             H    H  O CH.sub.3 O                                                                          CH.sub.3     N                              SO.sub.2 (CH.sub.3)                                                                             H    H  O CH.sub.3 O                                                                          CH.sub.3 O   N                              SO.sub.2 (CH.sub.3)                                                                             H    H  O CH.sub.3                                                                            CH.sub.3     N                              SO.sub.2 (CH.sub.3)                                                                             H    H  O CH.sub.3 O                                                                          CH.sub.3     N                              SO.sub.2 (CH.sub.3)                                                                             H    H  O CH.sub.3 O                                                                          CH.sub.3 O   N                              F                 7-CH.sub.3 O                                                                       H  S CH.sub.3                                                                            CH.sub.3 O   CCH.sub.3                      F                 2-CH.sub.3                                                                         H  O CH.sub.3                                                                            CH.sub.3 O   CH                             F                 H    CH.sub.3                                                                         O CH.sub.3 O                                                                          CH.sub.3 OCH.sub.2                                                                         CH                             Br                3-CH.sub.3 O                                                                       H  S CH.sub.3                                                                            CH.sub.3 CH.sub.2 OCH.sub.2                                                                N                              Br                H    H  O CH.sub.3 O                                                                          CH.sub.3 O   CH                             Br                4-F  H  O CH.sub.3                                                                            CH.sub.3 CH.sub.2 CH.sub.2                                                                 CH                             CH.sub.3          6-OCH.sub.3                                                                        H  O CH.sub.3                                                                            OCH.sub.2 CO.sub.2 CH.sub.3                                                                N                              CH.sub. 3         5-Cl CH.sub.3                                                                         O CH.sub.3 O                                                                          OCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3                                                       CH                             CH.sub.3          H    H  S CH.sub.3 O                                                                          CH.sub.3     N                              SO.sub.2 N(CH.sub.3)(CH.sub.2 CH.sub.3)                                                         H    H  O CH.sub.3 O                                                                          CH.sub.3 O   CH                             SO.sub.2 N(CH(CH.sub.3).sub.2)(CH.sub.2 CH.sub.3)                                               H    H  O CH.sub.3 O                                                                          CH.sub.3     N                              SO.sub.2 N(CH.sub.2 CH(CH.sub.3).sub.2)(CH.sub.2 CH.sub.2 CH.sub.3)                             5-NO.sub.2                                                                         H  S CH.sub.3 O                                                                           ##STR65##   N                              SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                             2-OCH.sub.3                                                                        H  O CH.sub.3                                                                             ##STR66##   CH                             SO.sub.2 N(CH.sub.3)(CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3)                                       4-Me CH.sub.3                                                                         O CH.sub.3 O                                                                          OCH.sub.2 CH.sub.3                                                                         CH                             SO.sub.2 N(OCH.sub.3)CH.sub.3                                                                   H    H  O CH.sub.3 O                                                                          CH.sub.3 O   CH                             SO.sub.2 N(OCH.sub.3)CH.sub.3                                                                   H    H  O CH.sub.3 O                                                                          CH.sub.3     CH                             SO.sub.2 N(OCH.sub.3)CH.sub.3                                                                   7-Cl H  S CH.sub.3                                                                            OCH(CH.sub.3).sub.2                                                                        N                              SO.sub.2 N(OCH.sub.3)CH.sub.3                                                                   5-NO.sub.2                                                                         CH.sub.3                                                                         O CH.sub. 3 O                                                                         OCH.sub.2 CHCH.sub.2                                                                       CH                             OSO.sub.2 (CH.sub.2 CH.sub.2 CH.sub.3)                                                          7-Br H  O CH.sub.3                                                                             ##STR67##   N                              OSO.sub.2 (CH(CH.sub.3)CH.sub.2 CH.sub.3)                                                       4-CH.sub.3                                                                         H  S CH.sub.3                                                                            CH.sub.3 O   CCH.sub.3                      OSO.sub.2 (CH(CH.sub.3).sub.2)                                                                  3-CH.sub.3 O                                                                       H  O CH.sub.3 O                                                                          CH.sub.3 O   CCH.sub.3                      OSO.sub.2 (CH.sub.3)                                                                            H    H  O CH.sub.3 O                                                                          CH.sub.3     N                              O(CH.sub.2 CH.sub.3)                                                                            7-NO.sub.2                                                                         H  O CH.sub.3                                                                            OCH.sub.3    CH                             O(CH.sub.3)       H    H  O CH.sub.3 O                                                                          CH.sub.3 O   CH                             O(CH.sub.2 CH(CH.sub.3).sub.2)                                                                  H    CH.sub.3                                                                         O CH.sub.3                                                                            CH.sub.3 O   CH                             O(CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3)                                                          4-Br H  O CH.sub.3 CH.sub.2 O                                                                 CH.sub.2 OCH.sub.3                                                                         N                              OSO.sub.2 CF.sub.3                                                                              H    H  O CH.sub.3 O                                                                          CH.sub.3     CH                             OSO.sub.2 CF.sub.3                                                                              H    H  O CH.sub.3 O                                                                          CH.sub.3 O   CH                             OSO.sub.2 CF.sub.3                                                                              5-F  H  S CH.sub.3                                                                            CH.sub.3     CCH.sub.3                      S(CH.sub.3)       2-F  H  S CH.sub.3 O                                                                          CH.sub.3     N                              S(CH.sub.3)       H    H  O CH.sub.3 O                                                                          CH.sub.3 O   CH                             S(CH(CH.sub.3).sub.2)                                                                           5-OCH.sub.3                                                                        H  O CH.sub.3                                                                            CH.sub.3 O   CH                             CO.sub.2 CH.sub.3 H    H  O CH.sub.3                                                                            CH.sub.3 O   N                              CO.sub.2 C.sub.2 H.sub.5                                                                        H    H  O CH.sub.3                                                                            C.sub.2 H.sub.5 O                                                                          N                              CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                                   H    H  O CH.sub.3                                                                            C.sub.2 H.sub.5 O                                                                          N                              CO.sub.2 CH.sub.2 CHCH.sub.2                                                                    H    H  O CH.sub.3                                                                            CH.sub.3     CH                             __________________________________________________________________________

                  TABLE IV                                                        ______________________________________                                         ##STR68##                                                                    A         A.sup.1 R.sup.4                                                                             W     R.sup.5                                         ______________________________________                                        NO.sub.2  H       H     O                                                                                    ##STR69##                                      NO.sub.2  H       H     O                                                                                    ##STR70##                                      NO.sub.2  H       H     O                                                                                    ##STR71##                                      NO.sub.2  H       H     O                                                                                    ##STR72##                                      NO.sub.2  H       H     O                                                                                    ##STR73##                                      NO.sub.2  H       H     O                                                                                    ##STR74##                                      NO.sub.2  H       H     O                                                                                    ##STR75##                                      NO.sub.2  H       H     O                                                                                    ##STR76##                                      SO.sub.2 (CH.sub.3)                                                                     H       H     O                                                                                    ##STR77##                                      SO.sub.2 (CH.sub.3)                                                                     H       H     O                                                                                    ##STR78##                                      SO.sub.2 (CH.sub.3)                                                                     H       H     O                                                                                    ##STR79##                                      SO.sub.2 (CH.sub.3)                                                                     H       H     O                                                                                    ##STR80##                                      SO.sub.2 (CH.sub.3)                                                                     H       H     O                                                                                    ##STR81##                                      SO.sub.2 (CH.sub.3)                                                                     H       H     O                                                                                    ##STR82##                                      SO.sub.2 (CH.sub.3)                                                                     H       H     O                                                                                    ##STR83##                                      SO.sub.2 (CH.sub.3)                                                                     H       H     O                                                                                    ##STR84##                                      Cl        H       H     O                                                                                    ##STR85##                                      Cl        H       H     O                                                                                    ##STR86##                                      Cl        H       H     O                                                                                    ##STR87##                                      Cl        H       H     O                                                                                    ##STR88##                                      Cl        H       H     O                                                                                    ##STR89##                                      Cl        H       H     O                                                                                    ##STR90##                                      Cl        H       H     O                                                                                    ##STR91##                                      Cl        H       H     O                                                                                    ##STR92##                                      ______________________________________                                    

                                      TABLE V                                     __________________________________________________________________________     ##STR93##                                                                    A.sup.2        A.sup.1                                                                            R.sup.4                                                                         W R.sup.6    X     Y         Z                          __________________________________________________________________________    Cl             H    H O CH.sub.3   CH.sub.3 CH.sub.2 O                                                                 H         CH                         Cl             H    H O CH.sub.3   CH.sub.3                                                                            CH.sub.3 O                                                                              CCH.sub.3                  Cl             H    H S CH.sub.3 CH.sub.2                                                                        CH.sub.3 O                                                                          CH.sub.3 OCH.sub.2                                                                      N                          Cl             H    H S CH.sub.3   CH.sub.3                                                                            CH.sub.3 O                                                                              CH                         Cl             H    H S CH.sub.3 CH.sub.2                                                                        CH.sub.3                                                                            CH.sub.3 O                                                                              N                          Cl             H    H S CH.sub.3   CH.sub.3 O                                                                          CH.sub.3 O                                                                              CH                         Br             8-NO.sub.2                                                                         H S CH.sub.2 CHCH.sub.2                                                                      CH.sub.3                                                                            CH.sub.3 CH.sub.2 OCH.sub.2                                                             N                          Br             8-NO.sub. 2                                                                        H S                                                                                ##STR94## CH.sub.3                                                                            OCH.sub.2 CO.sub.2 CH.sub.3                                                             N                          Br             H    H O CH.sub.3   CH.sub.3                                                                            CH.sub.3 O                                                                              CH                         F              5-OCH.sub.3                                                                        H S CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                             CH.sub.3                                                                            CH.sub.3  N                          F              H    H S CH.sub.3   CH.sub.3 O                                                                          CH.sub.3 O                                                                              CH                         F              H    H S CH.sub.2 CH.sub.2 CHCH.sub.2                                                             CH.sub.3                                                                            CH.sub.3  CH                         NO.sub.2       4-Cl H S                                                                                ##STR95## CH.sub.3 O                                                                          CH.sub.3 O                                                                              N                          NO.sub.2       H    H S CH.sub.3   CH.sub.3 O                                                                          CH.sub.3  CH                         NO.sub.2       H    H S                                                                                ##STR96## CH.sub.3                                                                            OCH.sub.2 CO.sub.2 CH.sub.2                                                   CH.sub.3  CH                         CH.sub.3       5-NO.sub.2                                                                         H S CH.sub.3   CH.sub.3                                                                            CH.sub.3 CH.sub.2 OCH.sub.2                                                             N                          CH.sub.3       H    H S CH.sub.3   CH.sub.3 O                                                                          CH.sub.3 O                                                                              CH                         CH.sub.3       8-NO.sub.2                                                                         H S CH.sub.3   CH.sub.3 O                                                                          CH.sub.3 CH.sub.2 CH.sub.2                                                              CH                         SO.sub.2 N(CH.sub.3)(OCH.sub.3)                                                              6-Br H O CH.sub.3   CH.sub. 3 O                                                                         CH.sub.3  N                          SO.sub.2 N(CH.sub.3)(OCH.sub.3)                                                              5-OCH.sub.3                                                                        H S CH.sub.3   CH.sub.3 O                                                                          CH.sub.3  CCH.sub.3                  SO.sub.2 N(CH.sub.3)(OCH.sub.3)                                                              H    H S CH.sub.3   CH.sub.3 O                                                                          CH.sub.3 O                                                                              CH                         OSO.sub.2 (CH.sub.2 CH(CH.sub.3).sub.2)                                                      3-Cl H S CH.sub.3   CH.sub.3                                                                            CH.sub.3 CH.sub.2 OCH.sub.2                                                             CH                         OSO.sub.2 (CH.sub.2 CH.sub.3)                                                                7-F  H S CH.sub.3 CH.sub.2 CH.sub.2                                                               CH.sub.3 CH.sub.2 O                                                                 CH.sub.3  CH                         OSO.sub.2 (CH.sub.3)                                                                         H    H S CH.sub.3 CH.sub.2                                                                        CH.sub.3                                                                            CH.sub.3 O                                                                              N                          O(CH.sub.3)    3-Cl H S CH.sub.3   CH.sub.3                                                                            CH.sub.3 O                                                                              CH                         O(CH.sub.3 CH.sub.2)                                                                         H    H S                                                                                ##STR97## CH.sub.3 O                                                                          CH.sub.3 O                                                                              CH                         O(CH.sub.3)    H    H S CH.sub.2 CHCH.sub.2                                                                      CH.sub.3                                                                            CH.sub.3  N                          S(CH.sub.3)    4-Br H S CH.sub.3   CH.sub.3 CH.sub.2 O                                                                 CH.sub.3  N                          S(CH.sub.3 CH.sub.2)                                                                         H    H O CH.sub.3   CH.sub.3                                                                            CH.sub.3 O                                                                              N                          S(CH.sub.3)    H    H S CH.sub.2 CHCHCH.sub.3                                                                    CH.sub.3                                                                             ##STR98##                                                                              CH                         SO.sub.2 (CH.sub.3)                                                                          H    H S CH.sub.3   CH.sub.3 O                                                                          CH.sub.3  CH                         SO.sub.2 (CH.sub.3)                                                                          H    H O CH.sub.3   CH.sub.3 O                                                                          CH.sub.3  N                          SO.sub.2 (CH.sub.3)                                                                          H    H S CH.sub.3 CH.sub.2                                                                        CH.sub.3 O                                                                          CH.sub.3 O                                                                              N                          SO.sub.2 (CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2)                                               H    H S CH.sub.3   CH.sub.3 CH.sub.2 O                                                                 CH.sub.3 CH.sub.2 OCH.sub.2                                                             CH                         SO.sub.2 (CH.sub.2 CH.sub.3)                                                                 H    H S CH.sub.2 CHCH.sub.2                                                                      CH.sub.3 O                                                                          CH.sub.3 OCH.sub.2                                                                      CH                         SO.sub.2 (CH(CH.sub.3).sub.2)                                                                4-Br H S                                                                                ##STR99## CH.sub.3                                                                            OCH.sub.2 CO.sub.2 CH.sub.2                                                   CH.sub.3  CH                         OSO.sub.2 CF.sub.3                                                                           H    H S CH.sub.3   CH.sub.3 O                                                                          CH.sub.3  CH                         OSO.sub.2 CF.sub.3                                                                           H    H S CH(CH.sub.3).sub.2                                                                       CH.sub.3 O                                                                          CH.sub.3  N                          SO.sub.2 N(CH.sub.3 (CH.sub.2 CH.sub.3)                                                      6-Br H S CH.sub.3   CH.sub.3 O                                                                          CH.sub.3  CH                         SO.sub.2 N(CH.sub.3 CH.sub.2)((CH.sub.3).sub.2 CH)                                           H    H O CH.sub.2 CH.sub.3                                                                        CH.sub.3                                                                            CH.sub.3 OCH.sub.2                                                                      CH                         SO.sub.2 N(CH.sub.3 CH.sub.2)(CH.sub.3)                                                      H    H S CH.sub.3   CH.sub.3 O                                                                          CH.sub.3 O                                                                              CH                         SO.sub.2 N(CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2)(CH.sub.3)                                    H    H S CH.sub.3   CH.sub.3                                                                            CH.sub.3 O                                                                              N                          __________________________________________________________________________

                                      TABLE VI                                    __________________________________________________________________________     ##STR100##                                                                   A                   A.sup.1                                                                            R.sup.4                                                                          W  R.sup.6    X      Y        Z                   __________________________________________________________________________    Cl                  H    H  O  CH.sub.3   CH.sub.3                                                                             CH.sub.3 O                                                                             CH                  Cl                  H    H  S  CH.sub.3   CH.sub.3                                                                             CH.sub.3 O                                                                             N                   Cl                  H    H  S  CH.sub.2CHCH.sub.2                                                                       CH.sub.3 O                                                                           CH.sub.3 O                                                                             N                   Cl                  H    H  S                                                                                 ##STR101##                                                                              CH.sub.3 O                                                                           CH.sub.3 O                                                                             CH                  Cl                  H    H  O  CH.sub.3   CH.sub.3                                                                             CH.sub.3 CH.sub.2                                                             OCH.sub.2                                                                              CH                  Cl                  H    H  S  CH.sub.3   CH.sub.3 CH.sub.2 O                                                                  CH.sub.3 CCH.sub.3           Br                  7-OCH.sub.3                                                                        H  S  (CH.sub.3).sub.2 CH                                                                      CH.sub.3 O                                                                           CH.sub.3 OCH.sub.                                                                      CH                  Br                  H    H  O  CH.sub.3   CH.sub.3                                                                             CH.sub.3 O                                                                             CH                  Br                  4-NO.sub.2                                                                         H  S  CH.sub.3   CH.sub.3                                                                             CH.sub.3 CH                  F                   2-CH.sub.3                                                                         H  S  CH.sub.3   CH.sub.3 O                                                                           CH.sub.3 N                   F                   H    H  S  CH.sub.2 CHCHCH.sub.3                                                                    CH.sub.3                                                                             OCH.sub.2 CO.sub.2                                                            CH.sub.3 CH                  F                   H    H  S                                                                                 ##STR102##                                                                              CH.sub.3                                                                             OCH.sub.2 CO.sub.2                                                                     CH                  CH.sub.3            6-OCH.sub.3                                                                        H  O  CH.sub.3   CH.sub.3 O                                                                           CH.sub.3 N                   CH.sub.3            5-Cl H  S  CH.sub.3 CH.sub.2                                                                        CH.sub.3 O                                                                           CH.sub.3 CH.sub.2                                                             OCH.sub.2                                                                              CH                  CH.sub.3            H    H  S  CH.sub.3 CH.sub.2 CH.sub.2                                                               CH.sub.3 CH.sub.2 O                                                                  CH.sub.3 CCH.sub.3           NO.sub.2            H    H  S  CH.sub.3   CH.sub.3 O                                                                           CH.sub.3 N                   NO.sub.2            H    H  S  CH.sub.3   CH.sub.3 O                                                                           CH.sub.3 O                                                                             CH                  NO.sub.2            H    H  S  CH.sub.3   CH.sub.3 O                                                                           CH.sub.3 CH                  NO.sub.2            4-OCH.sub.3                                                                        H  S  CH.sub.2 CH(CH.sub.3).sub.2                                                              CH.sub.3 O                                                                           OCH.sub.2 CO.sub.2                                                            CH.sub.3 CH                  NO.sub.2            7-Cl H  S  CH.sub.3   CH.sub.3 O                                                                           CH.sub.3 CH.sub.2                                                             CH.sub.2 CH                  NO.sub.2            4-Br H  S  CH.sub.3   CH.sub.3                                                                              ##STR103##                                                                            CH                  SO.sub.2 (CH.sub.3) H    H  O  CH.sub.2 CH.sub.3                                                                        CH.sub.3 O                                                                           CH.sub.3 CH                  SO.sub.2 (CH.sub.3) H    H  S  CH.sub.3   CH.sub.3 O                                                                           CH.sub.3 O                                                                             CH                  SO.sub.2 (CH.sub.3) H    H  S  CH.sub.3   CH.sub.3 O                                                                           CH.sub.3 O                                                                             N                   SO.sub.2 (CH(CH.sub.3).sub.2)                                                                     3-OCH.sub.3                                                                        H  S  CH.sub.2 CH.sub.3                                                                        CH.sub.3                                                                             CH.sub.3 O                                                                             CH                  SO.sub.2 (CH.sub.2 CH.sub.3)                                                                      2-F  H  S  CH.sub.2 CHCH.sub.2                                                                      CH.sub.3 CH.sub.2 O                                                                  CH.sub.3 O                                                                             N                   SO.sub.2 (CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3)                                                    7-Cl H  S  CH.sub.3   CH.sub.3 O                                                                           CH.sub.3 O                                                                             CH                  SO.sub.2 (CH.sub.3) 5-OCH.sub.3                                                                        H  O                                                                                 ##STR104##                                                                              CH.sub.3                                                                             CH.sub.3 O                                                                             N                   SO.sub.2 (CH.sub.3) H    H  S  CH.sub.3   CH.sub.3 O                                                                           CH.sub.3 CH                  SO.sub.2 (CH.sub.2 CH.sub.3)                                                                      2-CH.sub.3                                                                         H  S  CH.sub. 3  CH.sub.3 O                                                                           OCH.sub.2 OCH.sub.2                                                           CH.sub.3 CH                  SO.sub.2 (CH.sub.3) 7-NO.sub.2                                                                         H  O  CH.sub.3   CH.sub.3 O                                                                            ##STR105##                                                                            N                   SO.sub.2 (CH.sub.3) H    H  S  CH.sub.3   CH.sub.3                                                                             CH.sub.3 O                                                                             CH                  SO.sub.2 (CH(CH.sub.3).sub.2)                                                                     5-Br H  S  CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                      CH.sub.3 O                                                                           CH.sub.3 O                                                                             N                   SO.sub.2 (CH.sub.3) 7-Br H  S  CH.sub.3   CH.sub.3 O                                                                           OCH.sub.2 CO.sub.2                                                            CH.sub.3 N                   SO.sub.2 (CH.sub.3) H    H  S  CH.sub.3   CH.sub.3 O                                                                           CH.sub.3 CH                  SO.sub.2 (CH.sub.2 CH.sub.2 CH.sub.3)                                                             3-CH.sub.3 O                                                                       H  S                                                                                 ##STR106##                                                                              CH.sub.3 O                                                                           OCH.sub.2 CH.sub.3                                                                     N                   SO.sub.2 (CH.sub.3) H    H  S  CH.sub.3   CH.sub.3                                                                             CH.sub.3 O                                                                             N                   SO.sub.2 (CH.sub.3) 4-CH.sub.3                                                                         H  S  CH.sub.3   CH.sub.3 O                                                                           CH.sub.3 O                                                                             CH                  SO.sub.2 (CH.sub.3) H    H  O  CH.sub.3   CH.sub.3 O                                                                           CH.sub.3 CH                  SO.sub.2 N(OCH.sub.3 )(CH.sub.3)                                                                  H    H  S  CH.sub.3   CH.sub.3                                                                             CH.sub.3 O                                                                             CH                  SO.sub.2 N(OCH.sub.3)(CH.sub.3)                                                                   H    H  S  CH.sub.3   CH.sub.3 O                                                                           CH.sub.3 O                                                                             CCH.sub.3           SO.sub.2 N(OCH.sub.3)(CH.sub.3)                                                                   H    H  S  CH.sub.2 CH.sub.3                                                                        CH.sub.3 O                                                                           CH.sub.3 N                   SO.sub.2 N(CH.sub.3)(CH.sub.2 CH.sub.3)                                                           H    H  S  CH.sub.3   CH.sub.3 O                                                                           CH.sub.3 OCH.sub.2                                                                     CH                  SO.sub.2 N(CH.sub.3 CH.sub.2 CH.sub.2)(CH.sub.3)                                                  H    H  S  CH.sub.3   CH.sub.3                                                                             CH.sub.3 O                                                                             N                   SO.sub.2 N(CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2)(CH.sub.2 CH.sub.2             CH.sub.3)           H    H  S  CH.sub.3   CH.sub.3 O                                                                           CH.sub.3 O                                                                             CH                  __________________________________________________________________________

                                      TABLE VII                                   __________________________________________________________________________     ##STR107##                                                                   QR.sup.8   A.sup.1                                                                           W R.sup.4                                                                          X   Y         Z                                           __________________________________________________________________________    OCH.sub.3  H   O H  CH.sub.3                                                                          H         CH                                          OCH.sub.3  8-F O H  H   CH.sub.3  CH                                          OCH.sub.3  8-Cl                                                                              O H  OCH.sub.3                                                                         OCH.sub.3 N                                           N(CH.sub.3).sub.2                                                                        8-Br                                                                              O H  CH.sub.3                                                                          OCH.sub.3 CH                                          N(CH.sub.3).sub.2                                                                        8-NO.sub.2                                                                        O H  CH.sub.3                                                                          OCH.sub.3 CH                                          OCH.sub.3  5-CH.sub.3                                                                        O H  CH.sub.3                                                                          OCH.sub.3 CCH.sub.3                                   OCH.sub.3  5-CH.sub.3                                                                        O H  CH.sub.3                                                                          CH.sub.3  CCH.sub.3                                   OCH.sub.2 CH.sub.2 OCH.sub.3                                                             5-Cl                                                                              O H  CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                        CH                                          OC.sub.2 H.sub.5                                                                         6-Cl                                                                              S H  CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                      CH                                          SCH.sub.3  H   O H  CH.sub.3                                                                          OCH.sub.2 OC.sub.2 H.sub.5                                                              N                                           SCH.sub.3  H   S H  CH.sub.3                                                                          OCH.sub.2 OCH.sub.3                                                                     N                                           OC.sub.2 H.sub.5                                                                         H   S H  CH.sub.3                                                                          OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                          CH                                          OC.sub.2 H.sub.5                                                                         H   O H  CH.sub.3                                                                          OCH.sub.2 CO.sub.2 CH.sub.3                                                             CH                                          OC.sub.2 H.sub.5                                                                         H   O H  CH.sub.3                                                                          OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                      CH                                          OCH.sub.3  H   O CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3 N                                           OC.sub.2 H.sub.5                                                                         H   O CH.sub.3                                                                         OCH.sub.3                                                                         N(CH.sub.3).sub.2                                                                       N                                           OCH.sub.3  5-Cl                                                                              O CH.sub.3                                                                         OCH.sub.3                                                                         CH.sub.3  CH                                          SCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3                                                    6-Cl                                                                              O CH.sub.3                                                                         OCH.sub.3                                                                         OC.sub.2 H.sub.5                                                                        CCH.sub.3                                   SCH.sub.3  3-CH.sub.3                                                                        O CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3 N                                           OCH.sub.3  H   O H  CH.sub.3                                                                          OCH.sub.2 COOCH.sub.3                                                                   CH                                          OCH.sub.2 CH.sub.2 Cl                                                                    H   O H  OCH.sub.3                                                                         OCH.sub.2 COOC.sub.2 H.sub.5                                                            CH                                          OCH.sub.3  H   O H  CH.sub.3                                                                          OCH.sub.2 COOC.sub.2 H.sub.5                                                            CH                                          On-C.sub. 3 H.sub.7                                                                      H   S H  OCH.sub.3                                                                         CH.sub.3  CH                                          N(C.sub.3 H.sub.7).sub.2                                                                 H   S H  OCH.sub.3                                                                         OCH.sub.3 CH                                          SC.sub.2 H.sub.5                                                                         H   O H  OCH.sub.3                                                                         CH.sub.3  CH                                           ##STR108##                                                                              H   O H  OCH.sub.3                                                                         CH.sub.3  CH                                           ##STR109##                                                                              H   O H  OCH.sub.3                                                                         OCH.sub.3 N                                           OCH.sub.2 CH.sub.2 Cl                                                                    H   O H  OCH.sub.3                                                                         CH.sub.3  CCH.sub.3                                   OCH.sub.2 CH.sub.2 Cl                                                                    H   O H  OCH.sub.3                                                                         OCH.sub.3 CH                                          O(CH.sub.2).sub.5 CH.sub.3                                                               H   O H  OCH.sub.3                                                                         CH.sub.3  CH                                          O(CH.sub.2).sub.5 CH.sub.3                                                               H   O H  OCH.sub.3                                                                         OCH.sub.3 N                                            ##STR110##                                                                              H   O H  OCH.sub.3                                                                         OCH.sub.3 N                                           OCH.sub.3  4-Cl                                                                              S H  OCH.sub.3                                                                         CH.sub.3  N                                           OCH.sub.3  4-Cl                                                                              S H  OCH.sub.3                                                                         OCH.sub.3 N                                           Oi-C.sub.3 H.sub.7                                                                       H   O H  OCH.sub.3                                                                         CH.sub.3  N                                           Oi-C.sub.3 H.sub.7                                                                       H   O H  OCH.sub.3                                                                         OCH.sub.2 CHCH.sub.2                                                                    N                                           On-C.sub.4 H.sub.9                                                                       H   O H  OCH.sub.3                                                                         CH.sub.3  CCH.sub.3                                   On-C.sub.4 H.sub.9                                                                       H   O H  OCH.sub.3                                                                         OCH.sub.3 CCH.sub.3                                   OC.sub.2 H.sub.5                                                                         H   O H  OCH.sub.3                                                                         OCH.sub.3 CH                                          O(CH.sub.2).sub.5 CH.sub.3                                                               H   O H  CH.sub.3                                                                          OCH.sub.2 CO.sub.2 CH.sub.3                                                             CH                                          OCH(CH.sub.2).sub.4 CH.sub.3                                                             H   O H  CH.sub.3                                                                          CH.sub.3  CH                                           ##STR111##                                                                              H   O H  CH.sub.3                                                                          OCH.sub.3 CH                                           ##STR112##                                                                              H   O H  CH.sub.3                                                                          OCH.sub.3 CH                                           ##STR113##                                                                              H   O H  CH.sub.3                                                                          OCH.sub.3 CH                                           ##STR114##                                                                              H   O H  CH.sub.3                                                                          OCH.sub.3 CH                                           ##STR115##                                                                              H   O H  CH.sub.3                                                                          OCH.sub.3 CH                                           ##STR116##                                                                              H   O H  CH.sub.3                                                                          OCH.sub.3 CH                                           ##STR117##                                                                              H   O H  CH.sub.3                                                                          OCH.sub.3 CH                                           ##STR118##                                                                              H   O H  CH.sub.3                                                                          OCH.sub.3 CH                                           ##STR119##                                                                              H   O H  CH.sub.3                                                                          OCH.sub.3 N                                            ##STR120##                                                                              H   O H  CH.sub.3                                                                          OCH.sub.3 N                                            ##STR121##                                                                              H   O H  CH.sub.3                                                                          OCH.sub.3 CH                                           ##STR122##                                                                              H   O H  CH.sub.3                                                                          OCH.sub.3 CH                                           ##STR123##                                                                              H   O H  CH.sub.3                                                                          OCH.sub.3 CH                                           ##STR124##                                                                              H   O H  CH.sub.3                                                                          OCH.sub.3 CH                                           ##STR125##                                                                              H   O H  CH.sub.3                                                                          OCH.sub.3 N                                            ##STR126##                                                                              H   O H  CH.sub.3                                                                          OCH.sub.3 N                                            ##STR127##                                                                              H   O H  CH.sub.3                                                                          OCH.sub.3 N                                            ##STR128##                                                                              H   O H  CH.sub.3                                                                          OCH.sub.3 N                                           __________________________________________________________________________

                                      TABLE VIII                                  __________________________________________________________________________     ##STR129##                                                                   A.sup.1                                                                           R.sup.6    QR.sup.8                                                                             X   Y        W                                          __________________________________________________________________________    5-Cl                                                                              CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          H        S N                                        6-Cl                                                                              CH.sub.3   OCH.sub.3                                                                            OCH.sub.3                                                                         OCH.sub.3                                                                              S N                                        6-Br                                                                              CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub.3                                                                              S N                                        5-Br                                                                              CH.sub.3   OC.sub.2 H.sub.5                                                                     CH.sub.3                                                                          OCH.sub.3                                                                              S N                                        8-Br                                                                              CH.sub.3   OC.sub.2 H.sub.5                                                                     OCH.sub.3                                                                         OCH.sub.3                                                                              O N                                        5-F CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                     O N                                        H   CH.sub.2 CH.sub.3                                                                        OC.sub.3 H.sub.7                                                                     CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                       S N                                        4-F CH.sub.3   OC.sub.3 H.sub.7                                                                     CH.sub.3                                                                          OCH.sub.3                                                                              S CH                                       8-CH.sub. 3                                                                       CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                     S CH                                       5-NO.sub.2                                                                        CH.sub.3   OC.sub.4 H.sub.9                                                                     CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                      O CH                                       4-CH.sub.3                                                                        CH.sub.3                                                                                  ##STR130##                                                                          CH.sub.3                                                                          OCH.sub.3                                                                              S CH                                       4-C.sub.2 H.sub.5                                                                 CH.sub.3                                                                                  ##STR131##                                                                          CH.sub.3                                                                          OCH.sub.2 CH.sub.2 CH.sub.3                                                            S CH                                       8-Cl                                                                              CH.sub.2 CH.sub.2 CH.sub.3                                                               N(CH.sub.3).sub.2                                                                    CH.sub.3                                                                          OCH.sub.3                                                                              S CCH.sub.3                                6-Cl                                                                              CH.sub.3   N(CH.sub.3).sub.2                                                                    CH.sub.3                                                                          OCH.sub.3                                                                              S CCH.sub.3                                8-CH.sub.3                                                                        CH.sub.3   SCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub.3                                                                              S CH                                       4-CH.sub.3                                                                        CH.sub.3   SCH.sub.3                                                                            CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                     S CH                                       5-Cl                                                                              CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          H        S N                                        6-Cl                                                                              CH.sub.3   OCH.sub.3                                                                            H   OCH.sub.2 CHCH.sub.2                                                                   S N                                        6-Cl                                                                              CH.sub.3   OCH.sub.3                                                                            OCH.sub.3                                                                         OCH.sub.3                                                                              S N                                        6-Br                                                                              CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub.3                                                                              S N                                        5-Br                                                                              CH.sub.3                                                                                  ##STR132##                                                                          CH.sub.3                                                                          OCH.sub.3                                                                              S N                                        5-Br                                                                              CH.sub.3   OCH.sub.3                                                                            OCH.sub. 3                                                                        OCH.sub.3                                                                              S N                                        3-Br                                                                              CH.sub.3   OCH.sub.3                                                                            OCH.sub.3                                                                         OCH.sub.3                                                                              S N                                        H   CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                       S N                                        3-F CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub.3                                                                              S N                                        5-F CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                     S N                                        H   CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                     S CH                                       6-F CH.sub.2 CH.sub.3                                                                        OCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub.2 CH.sub.3                                                                     S CH                                       5-NO.sub.2                                                                        CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                      S CH                                       4-CH.sub.3                                                                        CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub.3                                                                              S CCH.sub.3                                H   CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          CH.sub.3 S CH                                       2-Cl                                                                              CH.sub.2 CHCH.sub.2                                                                      OCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub.3                                                                              S CH                                       6-Cl                                                                              CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub.3                                                                              S CH                                       2-CH.sub.3                                                                        CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub.3                                                                              S CH                                       4-CH.sub.3                                                                        CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub.2 OCH.sub.3                                                                    S CH                                       6-Cl                                                                              CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          CH.sub.3 S CH                                       6-Cl                                                                              CH.sub.3   OCH.sub.3                                                                            OCH.sub.3                                                                         OCH.sub.3                                                                              S N                                        5-CH.sub.3                                                                        CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub.3                                                                              S N                                        6-CH.sub.3                                                                        CH.sub.2 CHCH.sub.2                                                                      OCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub.2 CO.sub.2 CH.sub.3                                                            S N                                        5-Br                                                                              CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub.2 OC.sub.2 CH.sub.3                                                            S N                                        5-CH.sub.3                                                                        CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          CH.sub.3 S N                                        5-NO.sub.2                                                                        CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub.2 CH.sub.3                                                                     S CH                                       4-Cl                                                                              CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                      S CH                                       6-CH.sub.3                                                                        CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                             OCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub.2 CHCH.sub.2                                                                   S CCH.sub.3                                4-F CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                     S CH                                       5-NO.sub.2                                                                        CH.sub.3   OCH.sub.3                                                                            OCH.sub.3                                                                         OCH.sub.3                                                                              S CH                                       5-Br                                                                              CH.sub.3   OCH.sub.3                                                                            OCH.sub.3                                                                         OCH.sub.3                                                                              S N                                        5-NO.sub.2                                                                        CH.sub.2 CHCH.sub.2 CH.sub.3                                                             OCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub.3                                                                              S N                                        5-F CH.sub.3   OCH.sub.3                                                                            OC.sub.2 H.sub.5                                                                  CH.sub.2 OCH.sub.3                                                                     S N                                        2-Cl                                                                              CH.sub.3   OCH.sub.3                                                                            OCH.sub.3                                                                         OCH.sub.3                                                                              S N                                        2-Cl                                                                              CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub.3                                                                              S N                                        2-CH.sub.3                                                                        CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub. 2 OCH.sub.3                                                                   S N                                        3-Cl                                                                              CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          OCH.sub.2 CO.sub.2 CH.sub.3                                                            S N                                        3-H CH.sub.3   OCH.sub.3                                                                            OCH.sub.3                                                                         OCH.sub.3                                                                              S N                                        3-Cl                                                                              CH.sub.3   OCH.sub.3                                                                            CH.sub.3                                                                          CH.sub.3 S N                                        __________________________________________________________________________

                                      TABLE IX                                    __________________________________________________________________________     ##STR133##                                                                   A.sup.1                                                                           R.sup.9 R.sup.4                                                                          W X      Y        Z                                            __________________________________________________________________________    H   CH.sub.3                                                                              H  O CH.sub.3 O                                                                           CH.sub.3 O                                                                             CH                                           H   CH.sub.3                                                                              H  O CH.sub.3                                                                             CH.sub.3 O                                                                             CH                                           H   CH.sub.3                                                                              H  O CH.sub.3                                                                             CH.sub.3 N                                            H   CH.sub.3                                                                              CH.sub.3                                                                         O CH.sub.3 O                                                                           CH.sub.3 CH                                           H   CH.sub.3                                                                              H  S CH.sub.3 O                                                                           CH.sub.3 O                                                                             N                                            8-CH.sub.3                                                                        CH.sub.3                                                                              H  O CH.sub.3 O                                                                           CH.sub.3 O                                                                             CH                                           5-Cl                                                                              CH.sub.3                                                                              H  O CH.sub.3 O                                                                           CH.sub.3 CH                                           8-Cl                                                                              CH.sub.3                                                                              H  S CH.sub.3 O                                                                           CH.sub.3 O                                                                             CH                                           8-NO.sub.2                                                                        CH.sub.3                                                                              H  O CH.sub.3                                                                             CH.sub.3 N                                            8-F CH.sub.3                                                                              H  O CH.sub.3 O                                                                           CH.sub.3 O                                                                             CCH.sub.3                                    5-Br                                                                              CH.sub.3                                                                              H  O CH.sub.3 O                                                                           CH.sub.3 CCH.sub.3                                    5-NO.sub.2                                                                        CH.sub.3                                                                              H  O CH.sub.3 O                                                                           CH.sub.3 O                                                                             N                                            H   C.sub.2 H.sub.5                                                                       H  O CH.sub.3 O                                                                           CH.sub.3 O                                                                             CH                                           H   C.sub.2 H.sub.5                                                                       H  S CH.sub.2 O                                                                           CH.sub.3 O                                                                             CH                                           H   C.sub.2 H.sub.5                                                                       CH.sub.3                                                                         O CH.sub.3 O                                                                           CH.sub.3 CH                                           8-CH.sub.3                                                                        C.sub.2 H.sub.5                                                                       H  O CH.sub.3 O                                                                           CH.sub.3 O                                                                             CH                                           H   CH.sub.3                                                                              H  O CH.sub.3 CH.sub.2 O                                                                  CH.sub.3 CH                                           H   C.sub.2 H.sub.5                                                                       H  O CH.sub.3                                                                             CH.sub.3 N                                            H   CH.sub.3CH.sub.2                                                                      H  O CH.sub.3                                                                             CH.sub.3 O                                                                             N                                            H   CH.sub.3 CH.sub.2 CH.sub.2                                                            H  O CH.sub.3 O                                                                           CH.sub.3 O                                                                             N                                            H   CH.sub.3 OCH.sub.2                                                                    H  O CH.sub.3                                                                             CH.sub.3 O                                                                             N                                                 ##STR134##                                                                           H  O CH.sub.3 O                                                                           CH.sub.3 O                                                                             N                                            H                                                                                  ##STR135##                                                                           H  O CH.sub.3 O                                                                           CH.sub.3 O                                                                             CH                                           H                                                                                  ##STR136##                                                                           H  O CH.sub.3 O                                                                           CH.sub.3 O                                                                             CH                                           4-Cl                                                                              CH.sub.3 CH.sub.2 CH.sub.2                                                            H  O CH.sub.3 O                                                                           CH.sub.3 N                                            8-Cl                                                                              CH.sub.3 CH.sub.2 CH.sub.2                                                            H  S CH.sub.3 O                                                                           CH.sub.3 O                                                                             CH                                           8-NO.sub.2                                                                         ##STR137##                                                                           H  O CH.sub.3 O                                                                           CH.sub.3 O                                                                             CCH.sub.3                                    8-CH.sub.3                                                                        CH.sub.3                                                                              H  O CH.sub.3                                                                             CH.sub.3 CH.sub.2 CH.sub.2 O                                                           N                                            H   CH.sub.3                                                                              H  O CH.sub.3                                                                             C.sub.2 H.sub.5 OCCH.sub.2                                                             CH                                           H   CH.sub.3 OCH.sub.2                                                                    H  O CH.sub.3 O                                                                           CH.sub.3 O                                                                             CH                                           H   CH.sub.3 OCH.sub.2                                                                    H  O CH.sub.3 O                                                                           CH.sub.3 N                                            H                                                                                  ##STR138##                                                                           H  O CH.sub.3 O                                                                           CH.sub.3 O                                                                             CH                                           __________________________________________________________________________

Additional analogs of Table IX wherein ##STR139## can be made by methodstaught herein.

                                      TABLE X                                     __________________________________________________________________________     ##STR140##                                                                   A.sup.1                                                                         T             R.sup.9      W R.sup.4                                                                          R.sup.5                                     __________________________________________________________________________    H NOCH.sub.3    CH.sub.3     O CH.sub.3                                                                          ##STR141##                                 H NOC.sub.2 H.sub.5                                                                            ##STR142##  O H                                                                                 ##STR143##                                 H NOCH(CH.sub.3).sub.2                                                                        (CH.sub.2).sub.5 CH.sub.3                                                                  O H                                                                                 ##STR144##                                 H NOCH.sub.2 CHCH.sub.2                                                                       CH.sub.2 CHCH.sub.2                                                                        O CH.sub.3                                                                          ##STR145##                                 H NOCH.sub.2 CHCHCH.sub.3                                                                     CH.sub.2 CHCHCH.sub.3                                                                      O H                                                                                 ##STR146##                                 H NOCH.sub.2 CHCH(CH.sub.2).sub.2 CH.sub.3                                                    CH.sub.2 CHCH(CH.sub.2).sub.2 CH.sub.3                                                     O H                                                                                 ##STR147##                                 H NOCH.sub.3                                                                                   ##STR148##  O H                                                                                 ##STR149##                                 H NOCH(CH.sub.3).sub.2                                                                         ##STR150##  O H                                                                                 ##STR151##                                 H NOCH.sub.3                                                                                   ##STR152##  O H                                                                                 ##STR153##                                 H NOCH.sub.2 CHCH.sub.2                                                                        ##STR154##  O H                                                                                 ##STR155##                                 H NOCH.sub.3                                                                                   ##STR156##  O H                                                                                 ##STR157##                                 H NOCH.sub.3                                                                                   ##STR158##  O H                                                                                 ##STR159##                                 H NOCH.sub.3                                                                                   ##STR160##  O H                                                                                 ##STR161##                                 H NOCH.sub.3                                                                                   ##STR162##  O CH.sub.3                                                                          ##STR163##                                 H NOCH.sub.3                                                                                   ##STR164##  O CH.sub.3                                                                          ##STR165##                                 H NOCH.sub.3                                                                                   ##STR166##  O CH.sub.3                                                                          ##STR167##                                 H NOCH.sub.3                                                                                   ##STR168##  O CH.sub.3                                                                          ##STR169##                                 __________________________________________________________________________

FORMULATIONS

Useful formulations of the compounds of Formula I can be prepared inconventional ways. They include dusts, granules, pellets, solutions,suspensions, emulsions, wettable powders, emulsifiable concentrates, andthe like. Many of these may be applied directly. Sprayable formulationscan be extended in suitable media and used at spray volumes of from afew liters to several hundred liters per hectare. High-strengthcompositions are primarily used as intermediates for furtherformulation. The formulations, broadly, contain about 0.1% to 99% byweight of active ingredient(s) and at least one of (a) about 0.1% to 20%surfactant(s) and (b) about 1% to 99.9% solid or liquid diluent(s). Morespecifically, they will contain these ingredients in the followingapproximate proportions:

                  TABLE X                                                         ______________________________________                                                    Active*                                                                       Ingredient                                                                            Diluent(s)                                                                              Surfactant(s)                                   ______________________________________                                        Wettable Powders                                                                            20-90      0-74     1-10                                        Oil Suspensions,                                                              Emulsions, Solu-                                                              tions (including                                                              Emulsifiable                                                                  Concentrates   3-50     40-95     0-15                                        Aqueous Suspensions                                                                         10-50     40-84     1-20                                        Dusts          1-25     70-99     0-5                                         Granules and                                                                  Pellets       0.1-95      5-99.9  0-15                                        High-Strength                                                                 Compositions  90-99      0-10     0-2                                         ______________________________________                                         *Active ingredient plus at least one of a surfactant or a diluent equals      100 weight percent.                                                      

Lower or higher levels of active ingredient can, of course, be presentdepending on the intended use and the physical properties of thecompound. Higher ratios of surfactant to active ingredient are sometimesdesirable, and are achieved by incorportion into the formulation or bytank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook ofInsecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books,Caldwell, N.J. The more absorptive diluents are preferred for wettablepowders and the denser ones for dusts. Typical liquid diluents andsolvents are described in Marsden, "Solvents Guide", 2nd Ed.,Interscience, New York, 1950. Solubility under 0.1% is preferred forsuspension concentrates; solution concentrates are preferably stableagainst phase separation at 0° C. "McCutcheon's Detergents andEmulsifiers Annual", MC Publishing Corp., Ridgewood, N.J., as well asSisely and Wood, "Encyclopedia of Surface Active Agents", ChemicalPublishing Co., Inc., New York 1964, list surfactants and recommendeduses. All formulations can contain minor amounts of additives to reducefoam, caking, corrosion, microbiological growth, etc.

The methods of making such compositions are well known. Solutions areprepared by simply mixing the ingredients. Fine solid compositions aremade by blending and, usually, grinding as in a hammer or fluid energymill. Suspensions are prepared by wet milling (see, for example,Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made byspraying the active material upon preformed granular carriers or byagglomeration techniques. See J. E. Browning, "Agglomeration", ChemicalEngineering, Dec. 4, 1967, pp. 147ff and "Perry's Chemical Engineer'sHandbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.

For further information regarding the art of formulation, see forexample:

H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16through Col. 7, line 19 and Examples 10 through 41.

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line43 through Col. 1, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58,132, 138-140, 162-164, 166, 167 and 169-182.

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 5,line 66 through Col. 5, line 17 and Examples 1-4.

G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc.,New York, 1961, pp. 81-96.

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., BlackwellScientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwiseindicated.

EXAMPLE 6

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        2-Chloro-N-[(4,6-dimethylpyrimidin-2-yl)-                                     aminocarbonyl]-1-naphthalene-                                                 sulfonamide                80%                                                sodium alkylnaphthalenesulfonate                                                                         2%                                                 sodium ligninsulfonate     2%                                                 synthetic amorphous silica 3%                                                 kaolinite                  13%                                                ______________________________________                                    

The ingredients are blended, hammer-milled until all the solids areessentially under 50 microns and then reblended.

EXAMPLE 7

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        2-Chloro-N-[(4,6-dimethoxypyrimidin-2-yl)-                                    aminocarbonyl]-1-naphthalene-                                                 sulfonamide                 50%                                               sodium alkylnaphthalenesulfonate                                                                          2%                                                low viscosity methyl cellulose                                                                            2%                                                diatomaceous earth          46%                                               ______________________________________                                    

The ingredients are blended, coarsely hammer-milled and then air-milledto produce particles of active essentially all below 10 microns indiameter. The product is reblended before packaging.

EXAMPLE 8

    ______________________________________                                        Granule                                                                       ______________________________________                                        wettable powder of Example 7                                                                          5%                                                    attapulgite granules   95%                                                    (U.S.S. 20-40 mesh; 0.84-0.42 mm)                                             ______________________________________                                    

A slurry of wettable powder containing ≈25% solids is sprayed on thesurface of attapulgite granules in a double-cone blender. The granulesare dried and packaged.

EXAMPLE 9

    ______________________________________                                        Extruded Pellet                                                               ______________________________________                                        2-Chloro-N-[(4-methoxy-6-methylpyrimidin-2-yl)-                               aminocarbonyl]-1-naphthalene-                                                 sulfonamide                25%                                                anhydrous sodium sulfate   10%                                                crude calcium ligninsulfonate                                                                             5%                                                sodium alkylnaphthalenesulfonate                                                                          1%                                                calcium/magnesium bentonite                                                                              59%                                                ______________________________________                                    

The ingredients are blended, hammer-milled and then moistened with about12% water. The mixture is extruded as cylinders about 3 mm diameterwhich are cut to produce pellets about 3 mm long. These may be useddirectly after drying, or the dried pellets may be crushed to pass aU.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S.No. 40 sieve (0.42 mm openings) may be packaged for use and the finesrecycled.

EXAMPLE 10

    ______________________________________                                        Oil Suspension                                                                ______________________________________                                        2-Chloro-N-[(4,6-dimethyl-1,3,5-triazin-2-yl)-                                aminocarbonyl]-1-naphthalene-                                                 sulfonamide              25%                                                  polyoxyethylene sorbitol hexaoleate                                                                     5%                                                  highly aliphatic hydrocarbon oil                                                                       70%                                                  ______________________________________                                    

The ingredients are ground together in a sand mill until the solidparticles have been reduced to under about 5 microns. The resultingthick suspension may be applied directly, but preferably after beingextended with oils or emulsified in water.

EXAMPLE 11

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        2-Chloro-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)-                               aminocarbonyl]-1-naphthalene-                                                 sulfonamide                 20%                                               sodium alkylnaphthalenesulfonate                                                                          4%                                                sodium ligninsulfonate      4%                                                low viscosity methyl cellulose                                                                            3%                                                attapulgite                 69%                                               ______________________________________                                    

The ingredients are thoroughly blended. After grinding in a hammer-millto produce particles essentially all below 100 microns, the material isreblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) andpackaged.

EXAMPLE 12

    ______________________________________                                        Low Strength Granule                                                          ______________________________________                                        2-Chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)                           aminocarbonyl]-1-naphthalene-                                                 sulfonamide                  1%                                               N,N-dimethylformamide        9%                                               attapulgite granules        90%                                               (U.S.S. 20-40 sieve)                                                          ______________________________________                                    

The active ingredient is dissolved in the solvent and the solution issprayed upon dedusted granules in a double cone blender. After sprayingof the solution has been completed, the blender is allowed to run for ashort period and then the granules are packaged.

EXAMPLE 13

    ______________________________________                                        Aqueous Suspension                                                            ______________________________________                                        2-Chloro-N-[(4,6-dimethoxypyrimidin-2-yl)amino-                               carbonyl]-1-naphthalene-                                                      sulfonamide                   40%                                             polyacrylic acid thickener    0.3%                                            dodecylphenol polyethylene glycol                                             ether                         0.5%                                            disodium phosphate            1%                                              monosodium phosphate          0.5%                                            polyvinyl alcohol             1.0%                                            Water                         56.7%                                           ______________________________________                                    

The ingredients are blended and ground together in a sand mill toproduce particles essentially all under 5 microns in size.

EXAMPLE 14

    ______________________________________                                        Solution                                                                      ______________________________________                                        2-Chloro-N-[(4-methoxy-6-methylpyrimidin-2-yl)-                               aminocarbonyl]-1-naphthalene-                                                 sulfonamide, sodium salt    5%                                                water                       95%                                               ______________________________________                                    

The salt is added directly to the water with stirring to produce thesolution, which may then be packaged for use.

EXAMPLE 15

    ______________________________________                                        Low Strength Granule                                                          ______________________________________                                        2-Chloro-N-[(4,6-dimethyl-1,3,5-triazin-2-yl)-                                aminocarbonyl]-1-naphthalene-                                                 sulfonamide                 0.1%                                              attapulgite granules        99.9%                                             (U.S.S. 20-40 mesh)                                                           ______________________________________                                    

The active ingredient is dissolved in a solvent and the solution issprayed upon dedusted granules in a double cone blender. After sprayingof the solution has been completed, the material is warmed to evaporatethe solvent. The material is allowed to cool and then packaged.

EXAMPLE 16

    ______________________________________                                        Granule                                                                       ______________________________________                                        2-Chloro-N-[(4,6-dimethoxypyrimidin-2-yl)-                                    aminocarbonyl]-1-naphthalene-                                                 sulfonamide                 80%                                               wetting agent               1%                                                crude ligninsulfonate salt (containing                                        5-20% of the natural sugars)                                                                              10%                                               attapulgite clay            9%                                                ______________________________________                                    

The ingredients are blended and milled to pass through a 100 meshscreen. This material is then added to a fluid bed granulator, the airflow is adjusted to gently fluidize the material, and a fine spray ofwater is sprayed onto the fluidized material. The fluidization andspraying are continued until granules of the desired size range aremade. The spraying is stopped, but fluidization is continued, optionallywith heat, until the water constant is reduced to the desired level,generally less than 1%. The material is then discharged, screened to thedesired size range, generally 14-100 mesh (1410-149 microns), andpackaged for use.

EXAMPLE 17

    ______________________________________                                        High Strength Concentrate                                                     ______________________________________                                        2-Chloro-N-[(4,6-dimethylpyrimidin-2-yl)amino-                                carbonyl]-1-naphthalene-                                                      sulfonamide                 99%                                               silica aerogel              0.5%                                              synthetic amorphous silica  0.5%                                              ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce amaterial essentially all passing a U.S.S. No. 50 screen (0.3 mmopening). The concentrate may be formulated further if necessary.

EXAMPLE 18

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        2-Chloro-N-[(4,6-dimethylpyrimidin-2-yl)amino-                                carbonyl]-1-naphthalene-                                                      sulfonamide                 90%                                               dioctyl sodium sulfosuccinate                                                                             0.1%                                              synthetic fine silica       9.9%                                              ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produceparticles essentially all below 100 microns. The material is siftedthrough a U.S.S. No. 50 screen and then packaged.

EXAMPLE 19

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        2-Chloro-N-[(4,6-dimethoxypyrimidin-2-yl)-                                    aminocarbonyl]-1-naphthalene-                                                 sulfonamide                 40%                                               sodium ligninsulfonate      20%                                               montmorillonite clay        40%                                               ______________________________________                                    

The ingredients are thoroughly blended, coarsely hammer-milled and thenair-milled to produce particles essentially all below 10 microns insize. The material is reblended and then packaged.

EXAMPLE 20

    ______________________________________                                        Oil Suspension                                                                ______________________________________                                        2-Chloro-N-[(4,6-dimethylpyrimidin-2-yl)-                                     aminocarbonyl]-1-naphthalene-                                                 sulfonamide                35%                                                blend of polyalcohol carboxylic                                               esters and oil soluble petroleum                                              sulfonates                 6%                                                 xylene                     59%                                                ______________________________________                                    

The ingredients are combined and ground together in a sand mill toproduce particles essentially all below 5 microns. The product can beused directly, extended with oils, or emulsified in water.

EXAMPLE 21

    ______________________________________                                        Dust                                                                          ______________________________________                                        2-Chloro-N-[(4-methoxy-6-methylpyrimidin-                                     2-yl)aminocarbonyl]-1-naphthalene-                                            sulfonamide                 10%                                               attapulgite                 10%                                               Pyrophyllite                80%                                               ______________________________________                                    

The active ingredient is blended with attapulgite and then passedthrough a hammer mill to produce particles substantially all below 200microns. The ground concentrate is then blended with powderedpyrophyllite until homogeneous.

UTILITY

The compounds of the present invention are active herbicides. They haveutility for broadspectrum pre- and/or post-emergence weed control inareas where complete control of all vegetation is desired, such asaround fuel storage tanks, ammunition depots, industrial storage areas,oil well sites, drive-in theaters, around billboards, highway andrailroad structures. By properly selecting rate and time of application,compounds of this invention may be used to modify plant growthbeneficially, and also selectively control weeds in crops such as riceand wheat.

The precise amount of the compound of Formula I to be used in any givensituation will vary according to the particular end result desired, theamount of foliage present, the weeds to be controlled, the soil type,the formulation and mode of application, weather conditions, etc. Sinceso many variables play a role, it is not possible to state a rate ofapplication suitable for all situations. Broadly speaking, the compoundsof this invention are used at levels of about 0.01 to 20 kg/ha with apreferred range of 0.1 to 10 kg/ha. In general, the higher rates ofapplication from within this range will be selected for adverseconditions or where extended persistence in soil is desired.

The compounds of Formula I may be combined with other herbicides and areparticularly useful in combination with3-(3,4-dichlorophenyl)-1,1-dimethylurea (diuron); the triazines such as2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine (atrazine); theuracils such as 5-bromo-3-sec-butyl-6-methyluracil (bromacil);N-(phosponomethyl)glycine (glyphosate);3-cyclohexyl-1-methyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione(hexazinone); N,N-dimethyl-2,2-diphenylacetamide (diphenamide);2,4-dichlorophenoxyacetic acid (2,4-D) (and closely related compounds);4-chloro-2-butynyl-3-chlorophenylcarbamate (barban);S-(2,3-dichloroallyl)diisopropylthiocarbamate (diallate);S-(2,3,3-trichloroallyl)diisopropylthiocarbamate (triallate);1,2-dimethyl-3,5-diphenyl-1H-pyrazolium methyl sulfate (difenzoquatmethyl sulfate); methyl 2-[4-(2,4-dichlorophenoxy)phenoxy]propanoate(diclofop methyl);4-amino-6-tert-butyl-3-(methylthio)-1,2,4-triazin-5(4H)one (metribuzin);3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (linuron);3-isopropyl-1H-2,1,3-benzothiodiazin-4(3H)-one-2,2-dioxide (bentazon);α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine (trifluralin);1,1'-dimethyl-4,4'-bipyridinium ion (paraquat); monosodiummethanearsonate (MSMA); 2-chloro-2',6'-diethyl(methoxymethyl)acetanilide(alachlor); and 1,1-dimethyl-3-(α,α,α-trifluoro-m-tolyl)urea(fluometuron).

The activity of these compounds was discovered in greenhouse tests. Thetests are described and the data resulting from them are shown below.

0=no effect

10=maximum effect

C=chlorosis or necrosis

D=defoliation

E=emergence inhibition

G=growth retardation

H=formative effects

6Y=abscised bud or flowers

TEST PROCEDURE A

Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), cassia (Cassia tora), morningglory(Ipomoea spp.), cocklebur (Xanthium spp.), sorghum, corn, soybean, rice,wheat and nutsedge tubers (Cyperus rotundus) were planted in a growthmedium and treated pre-emergence with a nonphytotoxic solvent solutionof the compounds of Table A. At the same time, cotton having five leaves(including cotyledonary ones), bush beans with the third trifoliate leafexpanding, crabgrass with two leaves, barnyardgrass with two leaves,wild oats with two leaves, cassia with three leaves (includingcotyledonary ones), morningglory with four leaves (including thecotyledonary ones), cocklebur with four leaves (including thecotyledonary ones), sorghum with four leaves, corn with four leaves,soybean with two cotyledondary leaves, rice with three leaves, wheatwith one leaf, and nutsedge with three-five leaves were sprayed with anonphytotoxic solvent solution of the compounds of Table A. Othercontainers of the above mentioned weeds and crops were treated pre- orpost-emergence with the same nonphytotoxic solvent so as to provide asolvent control. A set of untreated control plants was also included forcomparison. Pre-emergence and post-emergence treated plants and controlswere maintained in a greenhouse for sixteen days, then all treatedplants were compared with their respective controls and rated visuallyfor response to treatment. The data in Table A shows that the compoundsof this invention are very effective as herbicides and often causelittle or no injury to crops such as wheat and rice.

    TABLE A      POST-EMERGENCE          BARN-         BUSH- COT- MORNING- COCKLE-     NUTS- CRAB- YARD- WILD   SOY-  kg/ha BEAN TON GLORY BUR CASSIA EDGE     GRASS GRASS OATS WHEAT CORN BEAN RICE SORGHUM      ##STR170##      0.4 2C, 8G 2C,2H,5G 1C 2C, 9G 2C, 8G 1C, 5G 0 0 0 0 1C 2C, 9G 1C 2C, 9H      ##STR171##      0.4 6Y, 5C,8G 6C, 9G 9C 10C 9C 5C, 9G 2C 3C, 9H 1C 0 1C, 5H 5C, 9G 0 2G      ##STR172##      0.4 6Y, 9D9G 7C, 9G 9C 9C 5C, 9G 2C, 9G 0 2C, 3H 1C, 3G 1C 2C, 5G 9C     2C, 9G 2C, 9G      ##STR173##      0.4 6Y, 9D,9G 6C, 9G 9C 10C 9C 9C 2C, 5G 2C, 5H 1C, 6G 2C 7H 9C 1C, 3G     2C, 9G      ##STR174##      0.4 6Y, 3C,9G 2C, 6G 3C, 9G 9C 2C, 3G 0 3G 0 0 0 0 2C,2H,9G 1C, 3G 5G      ##STR175##      0.4 6Y, 5C,8G 5C, 9G 9C 6C, 9G 6C, 9G 1C, 8G 1C 2C, 7H 0 0 2C, 9H 2C,     9H 1C 2C, 9H       PRE-EMERGENCE        BARN-         MORNING-     YARD- WILD   SOY-     kg/ha GLORY COCKLEBUR CASSIA NUTSEDGE CRABGRASS GRASS OATS WHEAT CORN     BEAN RICE SORGHUM      ##STR176##      0.4 10E 8H 7G 3G 1C 3C 6G 3G 1C, 5G 2G 1C, 3G 1C, 8H      ##STR177##      0.4 9G 9H 1C, 8G 10E 2C, 5G 2C, 9H 3C 1C 1C, 8G 8H 6G 8H      ##STR178##      0.4 9C 9G, 9H 1C 10E 3G 2C, 6H 1C, 7G 0 1C, 7G 2C, 8H 3C, 9H 2C, 9H      ##STR179##      0.4 9G 9H 2C, 9G 9G 3C, 7G 3C, 8G 8G 6G 1C, 9G 2C, 9H 2C, 9H 4C, 9H      ##STR180##      0.4 5G 9H 5G 0 0 0 0 0 2G 2C 2C 0      ##STR181##      0.4 8G 9H 9G 10E 2C 3C, 9H 2C, 8G 1C, 2G 9H 2C, 8H 2C, 6H 2C, 9H

What is claimed is:
 1. A compound of the formula ##STR182## wherein A¹is H, F, Cl, Br, CH₃ O or NO₂ ;A is Cl, F, Br, NO₂, CH₃, --SO₂ NR¹ R²,--SO₂ N(CH₃)(OCH₃), --S(O)_(n) R³, -OR³, --OSO₂ R³ or OSO₂ CF₃ ; B is##STR183## n is 0, 1 or 2; R¹ is C₁ -C₄ alkyl; R² is C₁ -C₄ alkyl; R³ isC₁ -C₄ alkyl; R⁴ is H or CH₃ ; R⁵ is ##STR184## R⁶ is C₁ -C₆ alkyl; R¹⁰is H or CH₃ ; R¹¹ is C₁ -C₃ alkyl; R¹² is C₁ -C₃ alkyl or C₃ -C₆alkenyl; T is O or N-OR¹² ; W is O or S; X is CH₃, CH₃ O or CH₃ CH₂ O;X² is O or CH₂ ; Y is H, C₁ -C₃ alkyl, CH₃ OCH₂, CH₃ CH₂ OCH₂, OCH₂ CO₂--(H or C₁ -C₂ alkyl), OCH(CH₃)CO₂ (H or C₁ -C₂ alkyl), O--(C₁ -C₃alkyl), O--(C₃ -C₄ alkenyl) or NR¹⁰ R¹¹ ; Y¹ is H, CH₃ or OCH₃ ; Y² is Hor CH₃ ; and Z is N;and their agriculturally suitable salts.
 2. Acompound of claim 1 wherein ##STR185##
 3. A compound of claim 1 wherein##STR186##
 4. A compound of claim 2 wherein A is Cl, NO₂, CH₃, CH₃ O,CH₃ SO₂ O, CH₃ SO₂, SO₂ N(CH₃)₂, SO₂ N(CH₃)(OCH₃), CH₃ S or CH₃ SO.
 5. Acompound of claim 4 wherein A¹ is H.
 6. A compound of claim 5 wherein Yis CH₃ or CH₃ O, X² is O and Y² is CH₃.
 7. A compound of claim 6 whereinA is Cl.
 8. A compound of claim 3 wherein A² is Cl, NO₂, CH₃, CH₃ O, CH₃SO₂ O, CH₃ SO₂, SO₂ N(CH₃)₂, SO₂ N(CH₃)(OCH₃), CH₃ S or CH₃ SO.
 9. Acompound of claim 8 wherein A¹ is H.
 10. A compound of claim 9 whereinX² is O, Y is CH₃ or CH₃ O and Y² is CH₃.
 11. A compound of claim 10wherein A² is Cl.
 12. The compound of claim 1,2-chloro-N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide.13. The compound of claim 1,2-chloro-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide.14. The compound of claim 1,2-chloro-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide.15. The compound of claim 1,2-chloro-N-[(5,6-dihydro-4-methylfuro[2,3-d]pyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide.16. The compound of claim 1,2-chloro-N-[(5,6-dihydro-4-methoxyfuro[2,3-d]pyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide.17. The compound of claim 1,2-chloro-N-[(4,6-dimethylfuro[2,3-d]pyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide.18. The compound of claim 1,8-chloro-N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide.19. The compound of claim 1,8-chloro-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-naphthalene-sulfonamide.20. The compound of claim 1,8-chloro-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide.21. The compound of claim 1,8-chloro-N-[(5,6-dihydro-4-methylfuro[2,3-d]pyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide.22. The compound of claim 1,8-chloro-N-[(5,6-dihydro-4-methoxyfuro[2,3-d]pyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide.23. The compound of claim 1,8-chloro-N-[(4,6-dimethylfuro[2,3-d]pyrimidin-2-yl)aminocarbonyl]-1-naphthalenesulfonamide.24. A compound of the formula: ##STR187## wherein A¹ is H, F, Cl, Br,CH₃ O or NO₂ ;A² is ##STR188## Cl, F, Br, NO₂, --CH₃, --SO₂ NR¹ R²,--SO₂ N(CH₃) (OCH₃), --S(O)_(n) R³, --OR³, --OSO₂ R³ or --OSO₂ CF₃ ; Bis ##STR189## n is 0, 1 or 2; Q is O, S or NR⁷ ; R¹ is C₁ -C₄ alkyl; R²is C₁ -C₄ alkyl; R³ is C₁ -C₄ alkyl; R⁴ is H or CH₃ ; R⁵ is ##STR190##R⁶ is C₁ -C₆ alkyl; R⁷ is H, --OCH₃ or C₁ -C₄ alkyl; when Q is O or Sthen R⁸ is C₁ -C₆ alkyl; C₃ -C₆ alkenyl, CH₂ CH₂ OCH₃, CH₂ CH₂ OCH₂ CH₃,C₅ -C₆ cycloalkyl, C₄ -C₇ cycloalkylalkyl, phenyl, benzyl, or phenyl orbenzyl substituted with one or two groups selected from CH₃, Cl or OCH₃; and when Q is O, R⁸ may also be CH₂ CH₂ Cl; when Q is NR⁷ then R⁸ isH, C₁ -C₄ alkyl, C₃ -C₄ alkenyl and R⁸ and R⁷ taken together can be--(CH₂)₄ --, --(CH₂)₅ -- or --CH₂ CH₂ OCH₂ CH₂ -- with the proviso thatwhen R⁷ is CH₃ O, R⁸ is CH₃ ; R⁹ is C₁ -C₆ alkyl, C₃ -C₆ alkenyl, C₅ -C₆cycloalkyl, C₄ -C₇ cycloalkylalkyl, benzyl, benzyl substituted with oneor two groups selected from CH₃, Cl or OCH₃ ; R¹⁰ is H or CH₃ ; R¹¹ isC₁ -C₃ alkyl; R¹² is C₁ -C₃ alkyl or C₃ -C₆ alkenyl; T is O or N--OR¹² ;W is O or S; X is CH₃, CH₃ O or CH₃ CH₂ O; X² is O or CH₂ ; Y is H, C₁-C₃ alkyl, CH₃ OCH₂, CH₃ CH₂ OCH₂, OCH₂ CO₂ --(H or C₁ -C₂ alkyl),OCH(CH₃)CO₂ (H or C₁ -C₂ alkyl), O--(C₁ -C₃ alkyl), O--(C₃ -C₄ alkenyl)or NR¹⁰ R¹¹ ; Y¹ is H, CH₃ or OCH₃ ; Y² is H or CH₃ ; and Z is CH orCCH₃ ;and their agriculturally suitable salts.